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Fuel 86 (2007) 2679–2686

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Biodegradability of biomass pyrolysis oils: Comparison to

conventional petroleum fuels and alternatives fuels in current use
a,*
Joël Blin , Ghislaine Volle a, Philippe Girard a, Tony Bridgwater b, Dietrich Meier c

a
CIRAD Forestry Department, International Research Centre for Agricultural and Development, UPR Biomass Energy,
TA 10/16, 73, Avenue J.-F. Breton, 34398 Montpellier, Cedex 5, France
b
Aston University, Aston Triangle, B4 7ET, Birmingham, United Kingdom
c
BFH-Institute for Wood Chemistry, Leuschnerstrasse 91, D-21031 Hamburg, Germany

Received 29 November 2006; received in revised form 19 March 2007; accepted 20 March 2007
Available online 18 April 2007

Abstract

Concern with environmental issues such as global climate change has stimulated research into the development of more environmen-
tally friendly technologies and energy sources. One critical area of our economy is liquid fuels. Fast pyrolysis of lignocellulosic biomass
for liquids production is of particular concern, as it is one of the most interesting ways to produce renewable liquid fuel for transport and
heat and power production.
The aerobic biodegradability of various pyrolysis oils from different origins and of a EN 590 diesel sample was examined using the
Modified Sturm (OECD 301B). The results demonstrate that all fast pyrolysis oils assessed are biodegradable with similar shaped curves
with 41–50% biodegradation after 28 days, whereas the diesel sample reached only 24% biodegradation. Since pyrolysis oils achieved
biodegradability over 20% these are classified as inherently biodegradable. Modelling of biodegradation processes was successfully per-
formed with a first-order chemical reaction.
The biodegradability results obtained for biomass pyrolysis oils are compared to those of conventional and alternative fuels.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Biodegradation; Fast pyrolysis oil; Biofuel; Biomass

1. Introduction corresponds to the thermal conversion occurring in the

1.1. Fast pyrolysis
A wide variety of technologies are available to produce
energy from biomass. Biomass is the only renewable
resource that can be directly converted into liquid fuel, thus
providing a competitively priced fuel for transport, heat
and power production. Fast pyrolysis of biomass for liq-
uids production is of particular interest, as it is the only
thermal process that directly produces useable liquid prod-
uct from lignocellulosic biomass [1]. Literally, pyrolysis
*
Corresponding author. Fax: +33 4 67 61 65 15.
E-mail address: joel.blin@cirad.fr (J. Blin).
absence of oxygen. Biomass pyrolysis results in the produc-
tion of three products: gas, pyrolysis oil and charcoal [2,3].
The relative proportions of these products depend very
much on the pyrolysis method, the characteristics of the
biomass and the reaction parameters. Temperature, heat-
ing rate and vapour residence time can be adjusted to
favour charcoal or bio-oil productions [4].
Conventional carbonization or slow pyrolysis has slow
heating rates and long vapour residence time and is used
to maximise charcoal yields at around 35–40%, together
with around 30% liquid. In fast pyrolysis processes, very
high heating rate and short hot vapour residence time are
used to maximise the liquid product at around 75 wt% on
dry feed when the biomass is wood [5]. In both cases, the
thermo-decomposition of the biomass generates vapours

0016-2361/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.03.033
2680 J. Blin et al. / Fuel 86 (2007) 2679–2686
and aerosols [6,7]. After cooling, these condense to give a
dark brown mobile liquid composed of a very complex
mixture of oxygenated hydrocarbons with some water
[8–10]. While fast pyrolysis oils are single phase, slow
pyrolysis liquids are composed of two phase: an organic
fraction and an aqueous fraction.
Fast pyrolysis oil, commonly named bio-oil, has a heat-
ing value about half that of conventional fuel oil [11]. It can
substitute for fuel oil or diesel in many heat and power
applications [11–13]. Almost any form of biomass can be
considered for fast pyrolysis from agricultural wastes and
residues to annual and perennial energy crops.
1.2. Health and safety
The scale up of biomass pyrolysis technology and the
opportunity liquid may offers as concentrated bioenergy
carrier for large scale application, would expose a large
numbers of persons to potentials hazards. Diebold [14]
published the most extensive review on the toxicity of bio-
mass pyrolysis liquids. This paper reported on a significant
number of works done on hazards of acute and long term
exposure to ‘‘wood smoke and pyrolysis vapour’’ but none
on their eco-toxicity. However, with the increasing interest
in bio-oil, the health and safety aspects are of utmost
importance, including determination of their environmen-
tal impacts in the event of inadvertent problems or leaks
during transport, storage or processing. As biodegradation
is the dominant pathway for the environmental transfor-
mation of most chemicals, biodegradability properties of
bio-oils should be known to assess the impact of accidental
release [15,16]. Information on the kinetics of the degrada-
tion of a chemical substance in the environment is essential
for proper risk assessment and of primary importance to
apprehend the long-term effects of this substance. More-
over such data can also provide information on the product
behaviour for measures to adopt in case of large quantities
of spillage, in order to minimise adverse effect on human
health or ecosystem.
1.3. Biodegradability of bio-oil
To date, only one study on bio-oil biodegradation has
been published by Piskorz and Radlein [17]. They used a
non-standardized experimental method with a respirometer
to monitor the bio-oil biochemical oxygen demand in a
closed reactor over 5 days. The protocol they used, which
was developed for biochemical studies in activated sludge
process, is similar to the 5-days biochemical oxygen
demand (BOD5) norm [18] but their methods were further
developed in order to compare biodegradation kinetics of
wastes in water rather than to measure the ultimate biode-
gradability in controlled and standardized conditions [19].
In their study, Piskorz and all found that bio-oils are bio-
degradable, with biodegradation rates and patterns similar
to, but substantially higher than those for diesel fuel. The
aim of Piskorz and all was to assess the ultimate aerobic
biodegradability of pyrolysis oils in case of accidental dis-
charges. Results and conclusions are very interesting, but
as they used a non-standardized experimental method data
cannot be considered for the elaboration of MSDS.
In order to assess bio-oil biodegradability and to be able
to set up recommendations and MSDS, the biodegradabil-
ity of nine different fast pyrolysis bio-oils and one slow
pyrolysis oil was measured using the Modified Sturm test
301B [20,21] which is the conventional test used to assess
oil biodegradation [22–24]. The biodegradability results
obtained are discussed and compared with those of conven-
tional petroleum fuels and alternatives fuels in current use.
2. Materials and methods
2.1. Pyrolysis oils
Lignocellulosic biomass is a complex mixture of macro-
molecules or polymers (hemicellulose, cellulose, lignin) and
minor amounts of other organics which each pyrolyse or
degrade at different temperatures and by different mecha-
nisms and pathways [3,25,26]. The rate and extent of
decomposition of each of these components depends on
the process parameters (reactor temperature, biomass heat-
ing rate and pressure) [5].
Pyrolysis has received considerable creativity and inno-
vation in design reactor systems that provide the essential
ingredients of high heating rates, moderate reaction tem-
peratures and short hot vapour product residence times
for liquids. As a result, a large variety of reactor configura-
tions have been developed and are used by bio-oil produc-
ers [5,27,28].
Bio-oils collected to carry out this study were provided
by companies and research laboratories. These were
selected in order to study the influence of the process
parameters, such as the reaction temperature and the feed-
stock, on the biodegradability of the oil. The production
parameters and characteristics of these oils are given in
Table 1.
Nine fast pyrolysis oils (FPO) were produced by the
three main processes of fast pyrolysis: fluidised bed, circu-
lating fluidised bed and ablative reactors. The characteris-
tics of these reactors are described by Bridgwater et al.
[27,28].
Biodegradation of slow pyrolysis oil (SPO) was also
studied. This sample, which was produced in a fixed bed
reactor, was biphasic with 77 wt% aqueous fraction and
23 wt% organic fraction. In a first step the biodegradability
of the whole oil was studied. It was introduced into the
inoculated medium as an emulsion after being vigorously
stirred. In a second step, biodegradation of both the
organic (SPO-Org) and aqueous (SPO-Aq) fractions were
determined separately after decantation. The water content
of all samples was measured using the standard test method
ASTM D1744 by Karl Fisher titration; and elemental
CHN composition was determined using ASTM D5291-
92. The results of these measurements are presented in
 J. Blin et al. / Fuel 86 (2007) 2679–2686 2681

Table 1
Production parameters and characteristics of pyrolysis oils
Bio-oils Production parameters Chemical characteristics (on wet basis)
Reactor Reactor T C Biomass Water (% m/m) %C %H %N % Oa
FPO-1 Fluid bed 500 Beech 26.80 41.67 7.87 0.00 50.46
FPO-2 500 Miscanthus 24.60 43.13 8.14 0.22 48.51
FPO-3 500 Spruce 22.40 43.66 7.67 0.00 48.67
FPO-4 425 Spruce 26.70 39.37 7.64 0.37 52.62
FPO-5 600 Spruce 20.30 45.10 7.35 0.38 47.17
FPO-6 CFB 500 Beech 28.50 39.45 7.96 0.01 52.58
FPO-7 500 Forest residue 29.10 39.44 8.01 0.30 52.25
FPO-8 Ablative 480 Pine 24.90 41.27 7.79 0.01 50.93
FPO-9 560 Pine 37.00 32.64 8.30 0.35 58.71
SPO Fixed bed 500 Spruce 33.36 25.56 10.8 0.3 63.34
SPO-Org 28.60 62.54 7.59 0.00 29.87
SPO-Aq 67.8 14.88 11.46 0.4 73.26
CFB: circulating fluidised bed, FPO: fast pyrolysis oil, SPO: slow pyrolysis oil, Org: organic fraction, Aq: aqueous fraction.
a
By difference.

Table 1. The water contents varied between 20 and 37 wt%
which is due to the disparity in the moisture content of the
feedstocks used and the different technologies.
As pyrolysis oils can be used as a renewable energy
source to substitute for conventional fossil fuel in static
engine application, the aerobic biodegradation of a EN
590 diesel fuel was also studied. The diesel sample
contained 86.5 wt% carbon, 13.5 wt% hydrogen, and
0.005 wt% nitrogen.
2.2. Biodegradability test
The method used to evaluate the aerobic biodegradabil-
ity of pyrolysis oil was the OECD 301B Modified Sturm
Test for ready biodegradability [21,23]. This 28-day ulti-
mate aerobic biodegradation test was established for poorly
water-soluble compounds and it is the commonly test
selected to assess the biodegradation of petroleum products
[22,29,30]. The principle of the method involves addition of
a test material to a chemically defined liquid medium inoc-
ulated with wastewater micro organisms and aerated at
20–25 C. The OECD 301B Modified Sturm Test is the
more common test used to assess oil biodegradation
[22,24,31,32].
The biodegradation is quantified by trapping CO2
formed in the vessel during biodegradation. Carbon diox-
ide-free air is passed through the test solution, and the car-
bon dioxide released from bio-oxidation of the test material,
is reacted quantitatively in a solution of barium hydroxide.
The biodegradation (B) is calculated and expressed as a
percentage of the measured carbon dioxide, after subtract-
ing blank values, compared to the theoretical carbon diox-
ide (ThCO2) that would be generated if the tested material
were completely mineralized:
ðCO2 Þmaterial  ðCO2 Þblank
Bmaterial ¼ ; ð1Þ
ThCO2
where Bmaterial is the biodegradation of the tested material,
(CO2)material is the amount of CO2 measured in the test ves-
sel containing the material and (CO2)blank in blank control.
ThCO2 represents the amount of carbon dioxide formed
by complete oxidation of the organic carbon. If mmaterial is
the amount of the sample introduced in the tests vessel, C%
is the percentage of carbon in the sample, ThCO2 is calcu-
lated according to Eq. (2) [33].
44
ThCO2 ¼ mmaterial  C%  : ð2Þ
12
Because of the nature of the biodegradation process and of
the bacterial populations used as inoculum, all tests were
duplicated.
To test one oil, five flasks were necessary: two flasks con-
taining the oil to be tested in duplicate, two ‘‘blank’’ flasks
to characterize the inoculum respiration and one reference
flask containing sodium acetate to act as a control. The
experimental set-up consisted of 11 flasks to test four differ-
ent oils in parallel.
The inoculum source used for tests was activated sludge
freshly collected from the aeration tank of the sewage treat-
ment plant in St Gely du Fesc close to Montpellier
(France). This treatment plant receives predominantly
freshly collected domestic sewage and the activated sludge
has a concentration of 3.2 g l1 of suspended solids as rec-
ommended in the OECD guideline [21,34]. Fresh activated
sludge was collected one day prior to test initiation, and
homogenised in a blender for 30 min by stirring at medium
speed. After the sample settled the homogenized mass was
decanted, avoiding solids losses. A 10 ml l1 activated
sludge material was added to the test medium.
Sodium acetate was used as the reference compound to
check the procedure. It was tested in parallel in an appro-
priate vessel at the same time as the other test runs. A test is
considered valid if the percentage of degradation of the ref-
erence compound reached 60% biodegradation by day 14.
2682 J. Blin et al. / Fuel 86 (2007) 2679–2686

To estimate the biodegradability, the amount of oil

50
introduced into the flasks has to be precisely known, in
order to have around 15 mg l1 of dissolved organic com-
pounds (DOC) in the flask. Therefore, based on the oils’ 40

biodegradation rate [%]

elemental analysis, all tests were performed by introducing
the equivalent of 45 mg of carbon equivalent in the liquid
30
in 3 l of inoculum/mineral solution.
As pyrolysis oils are partially insoluble in water and
sticky, the sample to be introduced into the mineral med- 20
ium cannot be precisely weighted without losses. As recom-
mended by Morisier et al. [35] for this kind of substance, a
solid carrier was used. Pyrolysis oils were deposited and 10
weighed on non-biodegradable glass filters, before intro-
duction in the mineral medium. After 2 or 3 days stirring
0
in the inoculated medium, the filter breaks up into the ori- 0 5 10 15 20 25 30
ginal filament form and the entire oil sample is then
time [d]
released into the solution.
The CO2 emitted from the 11 flasks was periodically and Fig. 1. Biodegradation curves of fast pyrolysis oils: (m) FPO-1; (d) FPO-
individually measured during the 28 days period. On the 2; (j) FPO-3; () FPO-4; (n) FPO-5; (s) FPO-6; (h) FPO-7; (e) FPO-8;
28th day, 1 ml of concentrated hydrochloric acid was (·) FPO-9.
added to each vessel to drive off any remaining carbon
dioxide present in the test suspensions. On day 29, the last
measurement of carbon dioxide production was taken. 90

80
2.3. Results
70
biodegradation rate [%]

All oils were tested in duplicate as reported above except

60
SPO which was tested in four replicates because of its inho-
mogeneity. The sodium acetate used as the control, 50
degraded for all runs to approximately 69% (69.2%;
40
70.1%; 69.2%; 68.6%) by day 14, which validated the tests
and confirmed the viability of the microbial inoculums. The 30
reproducibility of the measurements is satisfactory since
the standard deviation between the four references is 7% 20

of the biodegradation. The average across the two repli- 10

cates cumulative biodegradation measured for each sample
as a function of time are plotted in Figs. 1 and 2. 0
0 5 10 15 20 25 30
As can be seen, all the pyrolysis oils tested were biode-
gradable as CO2 release was observed in every flask. As time [d]
shown on Fig. 1, all the fast pyrolysis oils tested have very Fig. 2. Biodegradation curves of slow pyrolysis oil, references and diesel:
similar biodegradation rates, with similar shaped curves (·) sodium acetate; (d) SPO-Aq; () SPO; (j) SPO-Org; (n) diesel.
and biodegradation between 41% and 50% after 28 days.
Surprisingly, despite fast pyrolysis oils being produced
phase reached 74% whereas the organic phase is only min-
using different conversion technologies and feedstocks,
eralized to 31%.
and consequently different chemical compositions [36],
Taking account of the relative proportions of the
these all have very similar biodegradation behaviour. Bio-
organic and aqueous fractions (respectively 23 wt% and
degradation curves show high degradation rates during
77 wt%), the biodegradability of SPO is equal to the sum
the first eight days followed by a second phase where the
of the biodegradabilities of the two phases as reported in
production of CO2 is reduced. Tests were stopped after
Eq. (3).
28 days as recommended in the OECD guideline, but it is
clear that biodegradation was not completed as the curves 77  BðSPO-AqÞ þ 23  BðSPO-OrgaÞ
had not reached a plateau. It would be interesting to con- BðSPOÞ ¼ : ð3Þ
100
tinue the tests for a longer period.
The slow pyrolysis sample achieves 62% biodegradation The difference between the biodegradability rates of fast
and is more easily mineralized by the bacteria than fast and slow pyrolysis oils can be explained by the different
pyrolysis oils (Fig. 2). The two slow pyrolysis oil fractions chemical nature of the two kinds of oil. Even if the same
have very different biodegradability: the SPO aqueous chemical families of compounds are present in both oils,
 J. Blin et al. / Fuel 86 (2007) 2679–2686 2683

theirs concentrations are significantly different. In slow

60
pyrolysis processes, the heating rate and flow of gas pro-
duced are low, so that the residence times of pyrolysis va-
pours in the reactor are high. This encourages secondary 50

biodegradation rate [%]

reactions (cracking and recombination) with production
of both light functionalised compounds and more stable 40
heavy organic compounds. Light functionalised com-
pounds are predominantly soluble in water whereas heavy 30
organic compounds are not, which results in phase
separation. 20
In the fast pyrolysis process, the residence times of
vapours are very short, minimising secondary reactions 10
[5]. Fast pyrolysis oils are mainly composed of functional-
ised organic compounds close to monomers of cellulose
0
and hemicelluloses together with cracked lignin polymers 0 5 10 15 20 25 30
known as pyrolytic lignin. time [d]
It has been established that high molecular weight, low
Fig. 3. Biodegradability of (n) FPO-2 and (s) SPO. Experimental values
water solubility and the presence of several aromatic rings
(points) and biodegradation curves are modelled following Eq. (3).
increases resistance to biodegradation [37,38]. This explains
the different biodegradation of the materials studied. It has
been found that bacteria more easily degrade light highly Table 2
functionalised compounds of SPO-Aq, than the organic Measured biodegradation and kinetics constants of first-order equation
describing biodegradation of pyrolysis oils and diesel
partially water soluble constituents of FPO and the more
stable heavy organic compounds of SPO-Org. Oils Measured Calculated
All pyrolysis oils, both slow and fast, are more biode- Bday 29 (%) Bmax (%) k (day1) tlag (days) T1/2 (days)
gradable than the Diesel sample (24%), which is mainly FPO-1 45.90 46.15 0.14 0.91 5.06
composed of branched chain alkanes, cycloalkanes, aro- FPO-2 44.25 43.86 0.14 1.09 5.00
matic hydrocarbons and mixed aromatic cycloalkanes. FPO-3 42.77 42.23 0.15 0.94 4.66
FPO-4 49.72 49.27 0.15 1.16 4.59
FPO-5 40.78 40.33 0.14 1.20 4.88
2.4. Modelling degradation curves FPO-6 44.64 44.75 0.15 1.03 4.69
FPO-7 43.29 43.34 0.15 1.47 4.60
In order to better characterize and quantify the ultimate FPO-8 50.11 51.13 0.13 1.04 5.17
FPO-9 49.50 49.14 0.17 1.66 4.02
aerobic degradation of pyrolysis oils, the experimental
SPO 62.25 62.08 0.18 0.74 3.87
cumulative curves were simulated with a first-order kinetics SPO-Org 30.63 30.73 0.13 1.13 5.20
equation (4) [39–41]. Carbon dioxide productions were SPO-Aq 74.02 73.93 0.16 1.53 4.25
regression-analysed by the least squares method, minimisa- Diesel 24.33 26.61 0.10 4.03 7.22
tion of target function applying the Solver subprogram of Bday 29: percentage biodegradation measured after 29 days, Bmax: calcu-
Microsoft Excel 2002 SP3 [42] lated maximum percentage biodegradation, k: rate constant (day1), tlag:

lag phase of biodegradation (day), T1/2: half-life time of biodegradation
BCO2 ¼ Bmax 1  ekðttlag Þ ; ð4Þ (day).

where BCO2 is the percentage biodegradation at time t

(days), Bmax is the maximum percentage biodegradation,
k is the rate constant (day1) and tlag is the lag phase of
biodegradation (day).
The half-life time of CO2 production T1/2 is obtained by
ln 2
T 1=2 ðdaysÞ ¼ tlag : ð5Þ
k bacteria from conventional inoculum sources.
Fig. 3 shows that biodegradation of pyrolysis oils can be
very well described by a first-order kinetic equation. The
kinetics parameters of the first-order models are numeri-
cally presented in Table 2.
The curves in Fig. 1, and the calculated kinetics data in
Table 2 show very low lag phases for all pyrolysis oils
(tlag  1 day). This corresponds to the inoculation period
at the beginning of the tests until biodegradation starts
[21]. For the Diesel sample a lag phase of 3–4 days was
observed. This time lag corresponds to the acclimatization
period for the bacteria fauna to develop competent degra-
der for effective degradation [24,31,43,44]. The fast biolog-
ical response factors towards pyrolysis oils can be
explained by the solubility of functionalised compounds
in the aqueous medium, which are quickly degraded by
Low lag phases for pyrolysis oil biodegradation, also
show that despite use of a glass filter as solid carrier, there
were no mass transfer limitations in the inoculated solu-
tion. Oils were rapidly dispersed in the bacteria medium
[40]. The CO2 produced was also rapidly released from
flasks and was not dissolved in the aqueous solution due
to the acidity of oils [43]. This was confirmed on day 29
when the addition of 1 ml of the acid solution released a
large amount of dissolved CO2 from only the reference
2684 J. Blin et al. / Fuel 86 (2007) 2679–2686

and diesel samples (which are not acidic) but not for the 28 day laboratory studies, due to its higher proportion of
bio-oil samples. high molecular weight aromatics [46,47]. Diesel and gaso-
To be classified as readily biodegradable as in the line, which are light crude oil derived fuels, are more biode-
OECD protocol, a compound must achieve at least 60% gradable and achieve up to 24–36% and 28% respectively.
of the ThCO2 within 28 days, and should reach that within Zhang et al. [44] used the test method EPA 560/6-82-003
10 days of achieving the first 10% of the ThCO2. Based on which is equivalent to the OECD 301B [45].
this definition, only the aqueous fraction of the SPO can be Morgan et al. [30] compared the biodegradability of a
classified as readily biodegradable. The slow pyrolysis sam- synthetic GTL diesel (gas-to-liquids) obtained by Fischer
ple can be classified as readily biodegradable but without Tropsch conversion of natural gas, and a crude oil derived
meeting the 10-day window criteria [23,24,34] and fast diesel fuel. Using the OECD 301B test the synthetic GTL
pyrolysis oils can be classified as inherently biodegradable diesel from Sasol reached 60% biodegradation in around
[45] since these oils achieved biodegradability over 20% 28 days whereas the crude oil derived diesel only degraded
based upon CO2 evolution within the 28 days. by 34%. The relatively good biodegradability of the syn-
thetic diesel is due to the low aromatic content in the
GTL fuel.
3. Comparison of the biodegradability of pyrolysis oils
Vegetables oils and their derived methyl esters have been
to conventional petroleum fuels and alternatives fuels
used as a diesel fuel substitute or additive for many years
in current use
and previous work has demonstrated that these are rapidly
degraded to reach biodegradation of between 76% and 90%
As pyrolysis oils can be used as a renewable energy
[44,48,49].
source to substitute conventional fossil fuels in burner or
In their studies Zhang et al. [44] have shown that vege-
heavy fuel in combustion engines, it is worthwhile to com-
tables oils are slightly less degraded than their modified
pare their biodegradation to those of petroleum products
methyl ester. This has been attributed to the higher viscos-
and others biofuels (Table 3).
ity of the vegetable oils and their limited solubility, which
As confirmed by the American Petroleum Institute [45]
limit their biodegradability.
very little data is available on the behaviour of fossil fuel
The results in Table 3 show that biodegradation of fast
oils in standard tests for biodegradability. Much of what
and slow pyrolysis oils is more effective and faster than that
is known is based on information gained from testing
of fossil fuel but not as good as that of vegetable oils.
hydrocarbon mixtures of other petroleum products.
Oil institutes generally agree that petroleum hydrocar-
The only values available in the literature are presented
bon biodegradability is governed by the molecular struc-
in Table 3. Heavy fuel oils are blended products based on
ture of individual hydrocarbons [50]. As explained before,
the residues from various refinery distillation and cracking
the simpler molecules are most readily degraded, while
processes. This fuel has low biodegradation of 11%, in
increased molecular weight, branching compounds and
Table 3
aromatic structures tend to decrease the biodegradation
Biodegradability data of fossils and bio fuels rate and sometimes the extent of biodegradation of hydro-
Fuels products Degradation References
carbons of the same carbon number [16]. Linear aliphatic
(28 days) alkanes of Fischer–Tropsch diesel and linear fatty acid in
Fossil fuels
vegetables oils or oil methyl ester are quite extensively bio-
Gas oil Commercial 24–36% Present study degraded, while branching and aromatic compounds of
[22,30,37,44,49] fossil fuels are more stable and less biodegradable.
Fischer Tropsch 60% [30] For a biochemical process to occur rapidly, appropriate
Gasoline 91 octane 28% [37] enzymes must be available [15]. Vegetable oil consists of
Heavy Bunker C oil 11% [46,47]
pure fatty acids; the enzymes responsible for their break-
fuel down exist naturally. Fatty acids are hydrocarbon chain
in ester form, with oxygen atoms attached which makes
Bio fuel them very biologically active. The enzymes responsible
Pyrolysis Fast pyrolysis oils 41–50% Present study for the dehydrogenation/oxidation reactions that occur in
oils
the process of degradation, recognize oxygen atoms and
Vegetable Refined rapeseed 83% [49] attack them immediately [44]. Moreover in many fossil
oils oil 78% [44] fuels the contents of heavy metals decreases microbial
Refined soybean 76% [44]
oil activities and thus decreases their biodegradability, which
is not the case for biofuel [51].
Methyl Rapeseed oil 87% [49]
esters methyl ester 88% [44]
Sunflower oil 90% [44] 4. Conclusions
methyl ester
Soybean oil methyl 85.4% [49] The study of the biodegradability of biomass pyrolysis
ester oils, show that this biofuel is biodegradable. According
 J. Blin et al. / Fuel 86 (2007) 2679–2686
minor adaptation the OECD 301B test method appears to
be suitable to assess the aerobic ultimate biodegradability
of these oils in fresh water.
Despite being produced using different conversion tech-
nologies and feedstocks, nine tested fast pyrolysis oils have
very similar biodegradation rates, with similar shaped
curves and biodegradation between 41% and 50% after
28 days. These can be classified as inherently
biodegradable.
Biodegradation curves show high degradation rates dur-
ing the first 8 days followed by a second phase where the
production of CO2 is reduced.
Modelling of the biodegradation of biomass pyrolysis
oils show that these can be very well described by a first-
order kinetic equation. Biodegradation starts immediately
with very short lag phases at the beginning of tests. This
indicates a very fast biological response and also reflects
a rapid mass transfer of oil from the glass filters to the solu-
tion, which validates the method used to introduce oil sam-
ples in test medium.
It would be very interesting to repeat these tests with a
more specialised source of inoculums. It is known that
inoculums from industrial wastewater treatment plants
generally show a higher biodegradation potential for the
chemical substances tested than inoculums from municipal
wastewater treatment plants. Inoculums from wastewater
treatment from oil industries or refinery plants should be
tested, as they have developed bacteria that have specially
adapted to break up cyclic and aromatic organics com-
pounds similar to those in bio-oils.
The biodegradability value of fast pyrolysis oils show
that in case of accidental spillages this fuel would be biode-
graded better than all fossil fuels, but not as well as vegeta-
bles oils.
Acknowledgements
The experimental tests were carried out in the frame-
work of an R&D project partially funded by the European
Commission through the Pyrolysis Network PyNe. We
appreciate the help of the fast pyrolysis liquids producers.
References
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