This workshop uses the example of a bio-based shampoo to demonstrate the use of biomass feedstocks, the bio-refinery concept, certification, and bio-based product standards.This version has been made for participants of the workshop, and is up to date as of November 2014. For the presenter version please visit http://www.slideshare.net/JamesSherwood2/bio-based-products-workshop-james-sherwood-nov-2014-presenter-version The purpose of this workshop is to provide an opportunity to learn about the various aspects of biomass use in the chemical industry. The chosen scenario is the production of a shampoo formulation. The participants are given a variety of numbered options concerning biomass selection and the types of certification that can be used. By the end of the workshop the participants will have filled in a 4-digit code with 48 possible solutions. The implications of each decision during the workshop can then be discussed. Provided to the participants in this handout are simplified versions of the presentation slides, along with detailed notes. At the end of the handout file is a breakdown of the different answers and some notes regarding the calculation of the various answers. Remember there is no correct answer - just have fun!

3. From ‘The Guardian’ (online, 13/10/14): Carney told a World Bank seminar on integrated
reporting on Friday [10th October 2014] that the “vast majority of reserves are unburnable” if
global temperature rises are to be limited to below 2 °C (the target proposed in the UN
Copenhagen Accord of 2009). This means two thirds of known fossil fuel reserves would be
written off, losing the potential income from their combined sale price of $28 trillion/£17.5
trillion (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 term
sustainable 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 radically
change its approach to production, consumption, processing, storage, recycling and disposal
of biological resources”. The action plan involves investment in research and policy making
for the development of the bio-based product market.
European efforts towards designing new standards, labelling and certification is presently
being undertaken in order to facilitate the growth of the European Bio-based market (see
www.kbbpps.eu and www.open-bio.eu for related research projects). These measures should
improve consistency and quality in the sector, reducing trade barriers and increasing
customer confidence. A standard is essentially an agreed way of doing something, often
published as a technical specification. This might be an agreed test method for the
determination of boiling points for example, or the criteria used to define sustainability.

5. The model product is loosely based on the
ingredients of a vanilla scented shampoo. Shampoo
and domestic cleaning products are typically dilute
surfactant solutions. The example in this workshop
has been designed to accentuate the outcomes of
the choice of biomass and different certification
options. The quantities of each ingredient are not
realistic quantities, and the amounts are based on
dry weight. Subsequent calculations are based on a
dry weight of 100 kg, representing one batch of the
formulation. If this was an actual product, it would
be diluted in water and sold in bottles much smaller
than 100 kg!
The glycerol is assumed to be bio-based (as the by-product
of bio-diesel production there tends to be a
surplus), while the proportion of biomass in both the
surfactant sodium laureth sulphate and vanillin are
chosen by you!

7. Biorefineries are not a new concept and in their current revival are developing with great
diversity. The categories assigned are rarely clear cut and sometimes the products and their
quantity are flexible. ‘Generations of biomass’ is a concept usually applied to the resulting
biofuels (e.g. a second generation biofuel). Here the meaning is used to describe the biomass
itself.
Biodiesel can be made on a small scale from virgin vegetable oil (1st generation biomass) or
used 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 in
the UK are in Hull and Teesside (refer to ECOFYS “UK biofuel industry overview” report, see
www.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 the
UK.
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 2nd
generation bio-refinery. Processes include hydrogenation (for isosorbide) and fermentation
(bio-ethanol).
Chemopolis is a lignocellulose biorefinery, using tree wood to produce cellulosic bio-ethanol
or paper depending on the market and economic advantage at any one time. Lignin is
converted to energy with a side-stream of fertiliser. Furfural and other small molecules are
also produced. Any lignocellulosic biomass is applicable, and this flexibility of feedstock
means Chemopolis is a 3rd generation bio-refinery.

8. The wheat crop is 58% straw, which although not directly used for food is useful as insulation
for protecting root vegetable crops such as carrots and as animal feed. Total wheat
production in the UK was 13 million metric tonnes in 2012 (see faostat.fao.org). Total straw
production in the UK exceeds 11 millions tonnes per annum including other cereal and
oilseed crops which represents a surplus (see ‘National and regional supply/demand balance
for agricultural straw in Great Britain’ by J. Copeland and D. Turley – ‘googleable’).
The wax can be extracted from the straw using solvents (including supercritical carbon
dioxide which is also used for the decaffeination of coffee). The wax is less than 2% of the
straw mass but contains fatty acids and fatty alcohols suitable for producing surfactants. The
dewaxed straw can then be used in a variety of applications. It can be burnt as a fuel and the
silicates recovered for use as composite binders, or potentially serve as the feedstock for
cellulosic ethanol bio-refineries.

9. 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 plant
produces up to 55 ktonne (70 million litres) of bioethanol per year, and uses around 650
ktonne of sugar beet (equivalent to around 110 ktonne of sugar) as the feedstock. The
Wissington biofuel plant is co-located next to an existing sugar plant which supplies 400
ktonne of sugar and 100 ktonne of dry animal feed per year, as well as a variety of other
products (including top soil and lime). The plant also captures the carbon dioxide from the
sugar fermentation which is sold to the food and drink sector. The site employs 240 people in
total, 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).

10. Sugar beet (sugar cane in more exotic places) is a high yielding sugar crop. The sugar can be
used in fermentation to produce bio-ethanol. However it is 1st generation biomass. The
waste streams from food sugar production can be useful feedstocks too, and have been
shown to be viable materials for producing plastics (e.g. PHA from molasses, see
www.dw.de/italian-company-makes-plastic-from-sugar-beet-waste/a-15438369). All the
sugar beet crop waste can be put to use in a 3rd generation biorefinery, creating a number of
opportunities.
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 of
additional chemical manufacturing processes. For the purpose of making the hydrophobic
tail of the surfactant sodium laureth sulphate, the oligomer of ethylene, dodecene, can be
hydrated 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.

12. 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 the
actual value is 4.7%. Furthermore, it was ruled in 2011 that biofuels contributing to European
renewable energy targets must be certified sustainable. This must apply to the actual biofuel
and 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 in
biofuel 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 gas
emissions (moving beyond the classic ‘food vs. fuel’ debate). “On 17th October 2012, the EC
published a proposal to limit global land conversion for biofuel production, and raise the
climate 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% was
achieved 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 was
agreed on 23rd October 2014 (see www.european-council.europa.eu/council-meetings?
meeting=f02588fd-757c-4697-a2cc-8af00f65ff7c&lang=en&type=European
Council). Nice pictures and graphs on this topic are available at
en.wikipedia.org/wiki/Renewable_energy_in_the_European_Union#Renewable_energy
_targets (note the UK and the Netherlands are doing pretty crap!)

13. 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. Hydrolysis
yields the fatty acids, which in turn may be hydrogenated and applied in the synthesis of
anionic surfactants such as sodium laureth sulphate. The infrastructure for producing
chemicals from vegetable oil is already in place because of biodiesel biorefineries.
Lauric acid (for sodium laureth sulphate production) is only abundant as part of the
triglycerides of coconut oil (~50%). It is not prevalent in rapeseed oil. The liberated fatty acids
of coconut oil have been used to make bio-based surfactants, typically featuring coco- in the
name, e.g. sodium coco sulphate and cocamidopropyl betaine). For more information on
surfactants based on renewable feedstocks, see
eu.wiley.com/WileyCDA/WileyTitle/productCd-0470760419.html# where the relevant
chapter of the book, ‘Surfactants from Renewable Resources’, is available to download for
free (true as of 27/10/14). We will (incorrectly) assume for the purpose of this workshop that
all the fatty acid groups of vegetable oils are suitable for producing surfactants with.

15. This is a very much simplified schematic of a biorefinery process using vegetable oil to
replace 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 the
conventional process requiring ethylene. Ethylene from naphtha is still used to produce the
ethylene 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 the
production of 50 kg of sodium laureth sulphate (dry mass).
The substitution of petrochemicals can be incomplete, and it can vary seasonally or
according to economic favourability. This is called a non-dedicated biorefinery. Harvest time
varies 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 (see
www.nesteoil.com/default.asp?path=1,41,538,2035,14053).

16. Now you can choose a number to go in the first box on your answer sheet. Imagine you operate a biorefinery
producing sodium laureth sulphate partially made from a biomass feedstock, as was shown on the previous
slide. Due to price competition (and maybe plant capacity limitations too) you cannot change over to a
completely bio-based feedstock. In order to produce the hydrophobic part of the surfactant, you have a
biomass feedstock budget of ‘6 credits’. However the price of the biomass varies seasonally (the blue bars on
the graph). It is cheapest in the autumn just after the harvest with 1 credit needed to purchase all the biomass
you need to maintain production of sodium laureth sulphate. The price increases steadily into the winter and
spring as reserves are depleted by demand. Storage costs will also accumulate. In the summer the price goes
down in reaction to the market holding out until the new harvest. You can choose one option from the
following 4 scenarios. When making your choice remember the final shampoo product (containing 50 kg of
sodium laureth sulphate in every 100 kg) is produced by a formulator after purchasing each ingredient from
different suppliers. The sodium laureth sulphate will be certified before formulation. Then that information is
used 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 time
except for in spring when the price is highest. On average biomass utilisation is high (75% of the maximum) but
for a quarter of the year the surfactant contains no biomass and could be misleading to consumers (although
bear in mind the glycerol and vanillin within the final shampoo formulation will impart some bio-based content
all year round).
Option 2: You can use biomass until the budget runs out, which means full biomass use in the autumn and
winter and for ¾ of the spring. Across the year the average is about two thirds of the maximum but again for
part 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 renewable
feedstock is used at all times. This means allowing for more biomass when it is cheap but reserving funds to use
a lower proportion of biomass when the feedstock is more expensive. With this option biomass feedstock
utilisation 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 in
advance to avoid going over budget! The total biomass utilisation is the lowest of the 4 options at 60%.

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

18. ISCC is one of many third party organisations offering biomass sustainability certification (for
biofuel sustainability schemes including one offered by ISCC, see
ec.europa.eu/energy/renewables/biofuels/sustainability_schemes_en.htm). The list of
criteria 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 the
sustainability of the biomass feedstock. The sustainability criteria do not apply to any
petrochemical or mineral feedstocks.
The amount of biomass incorporated into a bio-based product is not considered. This has
been 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 of
a greater requirement (e.g. in combination with the bio-based solvent standard FprCEN/TS
16766 which demands a minimum of 25% bio-based carbon content) does the proportion of
biomass in the product become relevant.

19. The use of renewable resources in the production of bio-based products can be accounted
for in many different ways. This this hypothetical example, 30% (by mass) of the feedstock is
biomass. The biomass is distributed across the numerous products in a way that might not
be well understood and vary with time. With allocation methods of bio-based content, that
biomass fraction can be assigned to whichever product (output) is deemed suitable as long
as the biomass content does not exceed the biorefinery input. Sometimes the certification
rules 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 exceed
the maximum feasible value. The result can be expressed as the amount of fossil resources
displaced 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 this
allocation approach one step further and performs the calculation using the calorific value of
the feedstocks, not their mass. The claimed fossil resource saving is therefore not directly
related to the mass of petrochemicals displaced. This can be demonstrated with the example
of sodium laureth sulphate made with the maximum amount of vegetable oil required to
produce the intermediate 1-dodecanol without using petrochemical ethylene and assuming
no losses throughout the process. The mass of biomass utilised is 68% of the organic
feedstock but only 37% of the total feedstock including water, oxygen sodium chloride and
hydrogen sulphide. The bio-based content that can be attributed to the sodium laureth
sulphate according to this method is 70%.

20. The method of ‘book and claim’ is exemplified in this workshop with the certification offered
by 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 the
process generally. If a chemical manufacturer is in possession of a certain quantity of
uncertified palm oil, they may purchase the certificates from an equal volume of palm oil
that has been certified as sustainable. The certificates are swapped and the palm oil that was
actually produced by sustainable methods is no longer considered as such. The same
procedure can be applied to other chemical feedstocks, and feasibly for a wider range of
transposed characteristics such as bio-based content.
RSPO has a variety of other ways it will certify palm oil as sustainable. These do not form part
of this workshop but are reviewed here briefly for completeness. The ‘conventional supply
chain’ of sustainable palm oil, from plantation to end product, can be certified if completely
traceable. The quantity of palm oil at the end of the supply chain is sustainable with no
contact having been made with uncertified palm oil.
When a known amount of certified sustainable palm oil is combined with a known amount of
uncertified palm oil, the end mixture may be divided into portions that reflect the original
input of sustainable palm oil. For example, 20 tonnes of sustainable palm oil might be mixed
with 80 tonnes of uncertified palm oil for transportation convenience. The mixture itself
cannot be claimed as sustainable or even as ‘20% sustainable’. Then 20 tonnes of the palm
oil mixture may be partitioned from the bulk and that aliquot designated as the sustainable
palm oil. This is the ‘allocated mass balance’ method and bears a resemblance to the
previous certification approach that also uses an allocation method.

21. If you chose to certify the feedstock for your second answer you now have the choice of
these three certification scheme types with which to fill in the third box on your answer
sheet (if you chose to certify the product for your second answer wait for now). For
clarification the options are as follows.
Sustainability: The biomass you use in the production of the surfactant must meet a long list
of sustainability criteria. There is no minimum amount of biomass required to validate the
certification.
Renewable resource use: The proportion of fossil resources displaced by biomass is
accounted 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-based
content of the product.
Book and claim: Your unsustainable biomass is redeemed by purchasing certificates
belonging to an equal volume of sustainably produced biomass. In doing so sustainable
practice is both funded and encouraged.

22. Previously the sustainability criteria and fossil resource savings have attributed qualities to a
bio-based product derived from the biomass feedstock. However it is possible to analyse the
finished product and produce a value for the bio-based content of that article. The premier
method of bio-based content analysis is radiocarbon analysis. If the ratio of 14C/12C isotopes
matches atmospheric levels all the carbon in the sample is bio-based. Intermediate values
between the modern radiocarbon abundance and that found in fossil reserves indicate
partially bio-based products. The precise bio-based carbon content of the sample can then
be 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 removed
with an acid pre-treatment before radiocarbon analysis. In the European equivalent (CEN/TS
16640) it is not and so there an be a discrepancy between the two approaches depending on
composition of the test material. These test methods, one off measurements, only apply to
products with a fixed quantity of bio-based carbon (products of dedicated bio-refineries). If
the proportion of biomass feedstock changes over time the product cannot be certified and
labelled with a specific bio-based carbon content.
The most accurate apparatus with which to determine carbon isotopic ratios is accelerator
mass 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 only
element that has a precise analytical method for determining whether it is fossil derived or
bio-based. Furthermore, in replacing fossil resources, consisting mainly of hydrocarbons,
displacing the petrochemical carbon with renewable carbon is most the battle.

24. The analysis of bio-based carbon content was discussed previously in the workshop. The
results of the radiocarbon analysis can be extended to the other elements in a bio-based
chemical. As demonstrated for sodium laureth sulphate, the atoms chemically bonded to
bio-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 the
slide). Deciding which carbons are bio-derived must be done on the basis of known reaction
chemistry pathways and an understanding of the feedstocks used, as is true when a
heteroatom is bound to both bio-based and fossil derived carbons. This methodology was
proposed by ACDV (see www.chimieduvegetal.com/pageLibre000110dd.asp). It does not
account for mineral derived atoms or the true origin of the non-carbon atoms. A true mass
balance (called ‘material balance’ here to distinguish it from other protocols) can incorporate
mineral derived atoms (framed in grey boxes).
The disparity between each approach is quite noticeable, with only the material balance
offering a true reflection of the actual bio-based content. However its calculation is
complicated and the result is not appealing when compared to the other methods. It is not
verified by analysis as the other two methods are, leaving it susceptible to errors, but it is
advantageous when the biomass input into a (non-dedicated) biorefinery fluctuates over
time 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, are
combined and the weighted sum of their bio-based content is used to produce a value for
the 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-based
content methodologies for your third answer. Refer back to the question summary for the
correct numbers to use.

26. 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 is
analogous to the contemporary petrochemical synthesis. Guaiacol is obtained from pine wood tar (see
www.chm.bris.ac.uk/motm/vanillin/vanillinh.htm). The reaction of guaiacol with glyoxylic acid (made from
petrochemical 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 cheaper
synthetic vanillin. A routine check is available using stable isotope ratios. Natural vanillin from vanilla beans has
an enrichment of 13C compared to synthetic products, even those using biomass feedstocks. Thus more
information is gained than radiocarbon analysis alone. Stable isotope ratios vary for a number of reasons. The
primary cause for differentiation in stable carbon isotopes is photosynthesis. Different plants have one of two
mechanisms 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 comes
from ancient plants all using C3-type photosynthesis (C4 is newer in evolutionary terms). Stable hydrogen
isotopic analysis can be used to help distinguish between petrochemical products and C3 plant (e.g. wheat) bio-based
products.
Cosmetics and personal care products can be certified ‘Organic’ by the USDA if the >95% of the ingredients
meet the criteria (excluding water and salt). Although certification and labelling exist for food products
generally (organic, fairtrade, etc.), differentiation between natural and ‘unnatural’ products is not the basis of a
special label. Guidelines are in place however for the use of the word natural on packaging, and changes to
these rules are persuading food producers to abandon ‘natural’ claims on processed foods (see
online.wsj.com/articles/SB10001424052702304470504579163933732367084).
Depending on how you perceive the added-value of these labels and claims, chose between natural vanillin and
synthetic vanillin options for your final answer.

28. The blue bars are the volume of material required just to produce the hydrophobic group for 50 kg of
surfactant (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-ethylene
price is particularly spurious and not commercially available anyway. It is unlikely to fall beneath the 10% price
increase 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 as
the lauric acid content of the triglycerides is negligible, and although using coconut oil is viable the necessary
data was not found.

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

30. This page has intentionally been left blank
James Sherwood
james.sherwood@york.ac.uk

43. Calculation results (1/6)
? X X X 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 savings
53% 48% 48% 42%
Applicable Y Y Y Y
Average bio-based carbon
content 50% 46% 45% 40%
? 2 4 X
Applicable
(i.e. does not vary with time)
N N N Y
Average total bio-based
content (atom connectivity)
43% 39% 39% 34%
? 2 5 X
Applicable
(i.e. never varies in a dedicated
facility)
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
? 1 2 X
? 2 6 X
Sodium laureth sulphate is 50% of the mass of the formulation so the values
above should be weighted appropriately to obtain their contribution to the
formulation. Sodium laureth sulphate is 51% carbon by mass.

44. Calculation results (2/6)
X 1 ? X Sustainability certification
? = 1 ? = 3
Biomass certification
Sustainability
criteria
Book and claim
Applicable to biomass as
feedstock
Y (e.g. RSPO) Y (e.g. RSPO)
Applicable to European bio-fuels Y N
Sustainability applicable to all
N (only the
parts of a bio-based product
biomass)
N (only the
biomass)
All the biomass must be sustainable and then the product is classifiable as
made from sustainable biomass. The proportion of biomass is not a factor
although if used in conjunction with other standards that can be applied to
specific products (bio-based solvents, etc.) minimum bio-based content
thresholds apply.
The ‘book-and-claim’ variety of sustainable biomass certification is not
always applicable. It is not allowed for bio-fuels within Europe, and at
present it is not included within draft standards addressing mass balance
claims for bio-based products. Therefore ‘book-and-claim’ sustainable
biomass may not be a viable route to certifying bio-based products.

45. Calculation results (3/6)
X 1 2 X Sustainability certification
Fossil resource savings can be calculated by assuming units of methane
equivalents for each calorific feedstock. This value is the lower heating
value of methane (50 MJ/kg) divided by that of the feedstock. The product
is assigned ‘allocation units’ by adding the individual feedstock masses
multiplied by their own methane equivalent values (*44 for sodium laureth
sulphate made from vegetable oil, the worked example is given below).
Total bio-based content is derived from the mass and calorific value of the
biomass feedstock(s). This can be applied to the individual ingredients of a
formulation, in turn to give a bio-based content for the complete article.
Contribution Bio-based content
Ingredient
Mass
/kg
CH4
eq.
Material
balance
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 equivalents
is the proportion of biomass feedstock(s) contributing to the assigned
methane equivalents of the intended product.

46. Calculation results (4/6)
X X X ? Vanillin source
? = 1 ? = 2
Vanillin origin Natural
Synthetic
(guaiacol)
Average fossil resource savings 100% 37%
Applicable Y Y
Average bio-based carbon content 100% 88%
Applicable
Y Y
(i.e. does not vary with time)
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 be
weighted appropriately to obtain their contribution to the formulation.
Vanillin is 63% carbon by mass.

47. Calculation results (5/6)
Other formulation
ingredients
Glycerol
Sodium
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

48. 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 of
feedstocks is usually enough in order to be able to reach a good estimate of
the 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 the
synthesis.
Heteroatoms (limited to hydrogen, nitrogen, and oxygen) bonded to the
bio-based carbon atoms are also considered bio-based. When multiple
carbon atoms are bonded to a heteroatom a knowledge of the synthetic
route is required to attribute the correct source to the heteroatom. Other
atoms (S, Na, Cl, etc.) are considered as bio-based.
The total bio-based content is reached by adding together the atomic
masses 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 a
total 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 final
article after reaction and processing losses contributes to the total mass of
the final product. The mass of the combined feedstocks must equal the
output 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).
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)
Whereas the two methods above only apply to dedicated biorefinery
products, for material balance an average (time-weighted) bio-based
content is permissible but the bio-based content may never drop to 0%.

49. Answer
Bio-based
carbon
content
Total bio-based
content
(atom
connectivity)
Total bio-based
content
(material
balance)
Sustainable
biomass?
Fossil
resource
saving (by
allocation)
Natural?
1 1 1 1 38% 35% 35% Yes 60% Yes
1 1 1 2 35% 31% 31% Yes 48% No
1 1 2 1 38% 35% 35% No 60% Yes
1 1 2 2 35% 31% 31% No 48% No
1 1 3 1 38% 35% 35% Yes 60% Yes
1 1 3 2 35% 31% 31% Yes 48% No
1 2 4 1 38% 35% 35% No 60% Yes
1 2 4 2 35% 31% 31% No 48% No
1 2 5 1 38% 35% 35% No 60% Yes
1 2 5 2 35% 31% 31% No 48% No
1 2 6 1 38% 35% 35% No 60% Yes
1 2 6 2 35% 31% 31% No 48% No
2 1 1 1 38% 35% 35% Yes 58% Yes
2 1 1 2 35% 31% 31% Yes 46% No
2 1 2 1 38% 35% 35% No 58% Yes
2 1 2 2 35% 31% 31% No 46% No
2 1 3 1 38% 35% 35% Yes 58% Yes
2 1 3 2 35% 31% 31% Yes 46% No
2 2 4 1 38% 35% 35% No 58% Yes
2 2 4 2 35% 31% 31% No 46% No
2 2 5 1 38% 35% 35% No 58% Yes
2 2 5 2 35% 31% 31% No 46% No
2 2 6 1 38% 35% 35% No 58% Yes
2 2 6 2 35% 31% 31% No 46% No
3 1 1 1 38% 35% 49% Yes 58% Yes
3 1 1 2 35% 31% 45% Yes 45% No
3 1 2 1 38% 35% 49% No 58% Yes
3 1 2 2 35% 31% 45% No 45% No
3 1 3 1 38% 35% 49% Yes 58% Yes
3 1 3 2 35% 31% 45% Yes 45% No
3 2 4 1 38% 35% 49% No 58% Yes
3 2 4 2 35% 31% 45% No 45% No
3 2 5 1 38% 35% 49% No 58% Yes
3 2 5 2 35% 31% 45% No 45% No
3 2 6 1 38% 35% 49% No 58% Yes
3 2 6 2 35% 31% 45% No 45% No
4 1 1 1 59% 52% 47% Yes 55% Yes
4 1 1 2 56% 48% 43% Yes 43% No
4 1 2 1 59% 52% 47% No 55% Yes
4 1 2 2 56% 48% 43% No 43% No
4 1 3 1 59% 52% 47% Yes 55% Yes
4 1 3 2 56% 48% 43% Yes 43% No
4 2 4 1 59% 52% 47% No 55% Yes
4 2 4 2 56% 48% 43% No 43% No
4 2 5 1 59% 52% 47% No 55% Yes
4 2 5 2 56% 48% 43% No 43% No
4 2 6 1 59% 52% 47% No 55% Yes
4 2 6 2 56% 48% 43% No 43% No
Results in black are in response to the choices made in the workshop. Those
in grey are applicable but not a consequence of the choices made.

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James Sherwood
james.sherwood@york.ac.uk