Newsletter 2
BIOCOUP started in May 2006. We have made
good progress, although the Supervisory Board*
has launched an internal mid-term evaluation so
as to optimise our Tasks and Deliverables to
achieve our goals. The SB will implement some
minor modifications during the last two years of
the project.
All sub-projects have been successful in reaching
their objectives so far. There are a few inevitable
delays in some tasks, but constructive solutions
have been found. With such a large pan-European
Consortium, good co-operation between the
partners is clearly essential. Thanks to the many
inter-SP meetings this has certainly improved.
This is also aided by the stability within the
Consortium and seeing the same familiar faces
each time. This is especially important for the
younger researchers and their attendance and
active participation at meetings is noted and
appreciated. Later on in this Newsletter, one of
the young researchers will give her own account
of her experiences. Descriptions of the technical
activities per Subproject can be found further on
in this Newsletter. Here we confine ourselves to
giving a short highlight per SP.
SP1 has developed pyrolysis oil production
integrated to a fluidized-bed boiler as shown
schematically here
In SP2, bio-oils have been upgraded with
incrementally varying process conditions as input
for evaluations in SP3. Strategies for reducing the
hydrogen consumption are being explored.
SP3. Co-processing of upgraded bio-oils using
standard hydrotreating or FCC catalysts and feeds
can give high hydrocarbon yields from a
lignocellulosic feed source.
SP4 evaluates the technical feasibility of the
identified isolation, fractionation and chemical
synthesis and bio-chemical synthesis technologies.
Fractions (aldehydes and phenolics) have been
isolated and the performance evaluation of bio-
liquid derived phenol formaldehyde resins in
particleboard applications performed.
Distillation
Purified
Phenolics
Bio-liquid
Phenol Fraction
Extraction
Distillation
Aldehyde Fraction Purified
Extraction
Aldehydes
Extraction Acid Fraction
Distillation
Disposal (boiler) Purified
Acids
Isolation
Fractionation
SP5. The first BIOCOUP base case, based on
results generated within the project, is being
evaluated.
In SP6, a coordinated effort in characterising bio
oils and intermediates is been carried out and
partners are continuously sharing their
experiences on bio oil characterisation. Alma’s
excellent project management deserves mention
in enabling this large Consortium to focus on the
technical advancements.
We have made considerable progress on several
fronts in the past 3 years of BIOCOUP. It is
important to keep this momentum going and
ensure that we not only achieve our objectives,
but also produce significant progress in the use of
pyrolysis oil and its upgrading to bio-
hydrocarbons.
Supervisory Board Chairman Colin Schaverien
Coordinator Yrjö Solantausta
* Chairman Colin Schaverien (Shell Global
Solutions Int.); members Yrjö Solantausta (VTT),
Kees Hogendoorn (University of Twente), André
B. de Haan (Technical University Eindhoven),
Claude Mirodatos (CNRS, Lyon)
Update on technical activities
SP1- Integration of bio-oil production to
existing biomass users: Compared to the more
traditional stand-alone fast pyrolysis approach,
the integrated concept has innovative features,
which need to be verified. In the integrated
concept either recycle gas or boiler flue gas may
be used instead of inert recycle gas. If boiler flue
gas is used, oxygen will be present in the
pyrolysis reactor. It is known that oxygen in
pyrolysis causes reduced organic yield and
increased water yield. When oxygen
corresponding to a typical content in fluidized bed
boiler flue gas was added to the fluidizing gas the
organic yield decreased by about 10 wt % and the
product liquid was markedly ‘aged’. This ageing
was seen as a decrease in carbonyl compounds
(aldehydes, ketones) and increase in water and
heavy material insoluble in water. The
consequences of aging are not known as of this
time concerning the final uses (=upgrading) of
this material. Three runs have been carried out
producing a total of about 1000 kg bio oil. These
bio oils are stored cold to prevent further
reactions.
SP2 - Develop smart upgrading strategies of
pyrolysis oils to enable co-processing: There
has been good progress on upgrading pyrolysis oil
by hydrodeoxygenation (HDO) with BTG, RuG and
UT producing upgraded oils using incremental
changes in operating conditions (T, P). For HDO
oils with high remaining oxygen levels (low HDO
severity), hydrogen consumption is relatively low,
which is beneficial with respect to economics.
Further reduction of hydrogen consumption might
be accomplished when using certain fractions
from pyrolysis oil. BIC is continuing their work on
catalyst development using model components.
Two separate PDUs will be built a) to produce
larger quantities (1 kg/hr) and study of the
operability and b) the influence of process
conditions on product quality will be studied (100
g/hr).
SP3: Co-processing of upgraded bio-oils in
archetypal refinery units - The upgraded bio-
oils from SP2 have been extensively evaluated in
both Fluidised Catalytic Cracking and
hydrotreating on a lab scale. In co-processing
these upgraded bio-oils with standard FCC feeds
such as a VGO (vacuum gas oil) or a Long
Residue, similar gasoline range yields, with only
slightly higher yields on coke and dry gas, are
obtained, compared to the FCC feed alone. This
suggests that the co-processing of upgraded bio-
oils using standard FCC conditions can afford bio-
hydrocarbons from a lignocellulosic feed source.
This SP also focuses on gaining fundamental
understanding from the study of model molecules.
The impact of the addition of these bio-oils and of
reaction temperature on the
hydrodesulphurisation (HDS) performance has
been studied. The hydrotreating of a mixture of
upgraded bio oils with SRGO confirms the
presence of phenolic degradation products related
to a decrease in desulphurization.
SP4: Selective separation of discrete target
oxygenates - Using the optimized isolation
procedure for aldehydes through the bisulphite
route TUE has produced a furfural containing
fraction from VTT pyrolysis oil (SP1). This fraction
was contained in the toluene used for the
recovery from the aqueous phase and delivered to
WP4.3 for further fractionation.
TUE has used the new Fischer Spaltrohr setup for
the production of 0.5 kg of a low toluene residue
furfural fraction, which is delivered to ARKEMA
(WP4.4) for solvent synthesis, and CHIMAR for
evaluation as additive in resin formulation in
WP4.5. Analysis by vTI has shown that compared
to the first generation aldehyde fraction the
toluene content has been reduced from 75% to
6.2%. Furthermore a small amount will be
delivered to CNRS for model studies in SP3. Due
to the high toxicity towards bacteria it was
decided that METEX would not evaluate these
multiple aldehyde fractions and focus on purified
single aldehydes, in particular glycoaldehyde.
CHIMAR has replaced 15% of phenol in
particleboard resins by VTT bio oil and
synthesized small quantities of resin based on the
first generation fractions delivered by NIC.
ARKEMA has selected the first product
applications of the bio-liquid derived oxygenated
target chemicals: solvents and adhesives.
SP5 -Evaluation of the technical, economic
and LCA (life-cycle analysis) performances:
A base case scenario analysis was carried out for
BIOCOUP during the previous period. The main
activity for the current period is the compilation
of, and the subsequent techno-economic
evaluation of, improved BIOCOUP production
chain(s) based on the new data and new process
ideas so far generated in the BIOCOUP project.
 FOCUS ON PYROLYSIS AT UNIVERSITY OF TWENTE
Fast pyrolysis is a technology for the conversion
of bulky solid biomass into a liquid with an energy
density (~ 17 MJ/kg) or approximately half that of
fossil oil. Several feedstocks are suitable for this
process, one of them being lignocellulosic biomass
which is not competing with the food chain. In
fast pyrolysis, organic material is heated rapidly to
450 - 500 0C in the absence of oxygen under
atmospheric pressure. A short residence time of
~ 2 s is required to obtain high oil yields. At these
conditions, biomass is converted to vapours
(~70%), permanent gases and char. After char
separation, the vapours are condensed to a dark
brown liquid known as pyrolysis or bio oil. The oil
consists of a complex mixture of oxygenated
components; the major groups of compounds
identified are water, hydroxyaldehydes,
hydroxyketones, sugars, carboxylic acids, and
phenolics. Possible applications for pyrolysis oil
include direct combustion, gasification eventually
followed by Fischer Tropsch synthesis, hydrogen
production, co-processing in refinery units in
order to produce transportation fuels and
extraction of chemicals. Besides the pyrolysis
process, in BIOCOUP the feasibility of co-
processing of (upgraded) pyrolysis oil and
extraction of chemicals from pyrolysis oil is
assessed technically and economically.
In BIOCOUP pyrolysis is carried out with two goals:
Firstly, to produce a uniform bio-oil feedstock for
all BIOCOUP partners. These partners use it either
for catalyst development, screening and testing or
for pyrolysis oil upgrading by techniques like High
Pressure Thermal Treatment, Catalytic
Decarboxylation or Hydrodeoxygenation. The
production of these relatively large quantities of
pyrolysis oil is carried out by VTT in Finland using
state of the art pyrolysis equipment. Secondly, at
the University of Twente (The Netherlands)
studies are carried out towards the further
improvement of the pyrolysis process by
application of an in-situ vapour filtration system.
In a conventional pyrolysis system some fine char
is inevitably entrained. Inorganics (defined as
ash) appear to be the centre of char formation
reactions. As ash is mainly incorporated within the
char fraction, the entrained solids fraction also
contains the ash. The presence of char/ash makes
pyrolysis oil unsuitable for direct combustion in
conventional oil/gas boilers and turbine
operations, because of fouling, corrosion, erosion
and plugging of orifices. Furthermore, char/ash
contributes to secondary cracking reactions in the
vapour phase thereby lowering the oil yield and
even it catalyzes (polymerization) reactions in the
oil at ambient conditions! This instability of
pyrolysis oil during storage is known under the
name “aging”. Aging is characterized by gradual
increase in the average molecular weight, thereby
also increasing viscosity and deteriorating product
quality. Finally, ash/char is expected to speed-up
poisoning and de-activation of the catalysts used
in catalytic upgrading processes as studied in
BIOCOUP. Rapid and complete char separation is
therefore desirable for a variety of reasons.
At the University of Twente, a novel system to
remove in-situ char/ash from hot pyrolysis
vapours has been developed and tested. For this,
a fluidized bed with immersed filters for in-situ
extracting pyrolysis vapors was designed and
built. The effect of in-situ hot pyrolysis vapour
filtration was studied with respect to process
stability, products yields and product quality. Oil
obtained via a more conventional cyclone system
placed in parallel to the filter system served as
reference for the quality and yields of the filtered
oil. Good process stability concerning temperature
and pressure drop across the hot gas vapour filter
was achieved The in-situ filtered oil contained
significantly less solids, alkali metals and ash as
compared to cyclone oil. The molecular weight of
the filtered oil obtained with non-dried feed was
always lower as compared to the cyclone oil (ΔMw
~ 20 g/mol). Results of the aging tests showed
that the reactivity of pyrolysis oil can already
originate from the highly reactive components in
pyrolysis oil itself and does not need the presence
of char/ash. In conclusion: hot gas vapour
filtration appears to be a promising technique to
reduce the ash and char content in pyrolysis oils.
However, the intrinsic reactivity of char/ash free
pyrolysis oil remains high.
 My experience as a young scientist in BIOCOUP
My name is Elly Hoekstra and I
am currently 27 years old. I grew
up in Heeze in Brabant (South of
the Netherlands) and then
studied Chemical Engineering at
the University of Twente. I
started my PhD in September
2006 within BIOCOUP in SP1.
More information about the content of my PhD is
written in this newsletter in “Focus on Pyrolysis”.
BIOCOUP gives me the opportunity to have input
in my research project from people working in
industry and university in disciplines like catalysis,
analysis and process engineering. For example,
VTT and vTI helped me a lot with analyzing the
pyrolysis oil.
The project also ensures diversity within my work:
meetings, workshops, tasks/ deliverables and
courses.
Coming Up in BIOCOUP
The mutual contact with other PhD students
within BIOCOUP is also very important for me.
Short communication routes are available to share
our problems and discuss solutions within the
research. And, of course, also the evenings after
the meetings we spend together having fun,
thereby also building up an international network
based on work and friendship. As an example, I
want to highlight the “Young Scientist Meeting” in
2007. The schedule for this one-week BIOCOUP
meeting was full of useful activities:
presentations, discussions, lab-days and company
excursions. We had an informative and inspiring
week (also busy and exhausting), and I am sure
that we have been able to use the knowledge and
energy from that week to the benefit for our work
within the BIOCOUP project!

TCB Biomass 2009 – International Conference on Thermochemical conversion science, Chicago

USA, September 16-18, 2009. Participation Upgrading and Pretreatment Panel Discussion
More details on http://media.godashboard.com//gti/TCBiomassBrochure.pdf

The 2nd Nordic Wood Biorefinery Conference, Finlandia Hall, Helsinki, Finland, September 2–4, 2009.
BIOCOUP presentations are planned on September 3
More details on: http://www.kcl.fi/page.php?page_id=499