to read the fourth Year Publishable Executive Summary - Biocoup

Publishable executive summary
Objectives
The aim of BIOCOUP is to co-process upgraded bio-liquids in conventional refinery units
and to selectively separate value-added chemicals. To achieve this, the Consortium has the
following scientific and technical objectives:
• To develop processes of primary fractionation and biomass liquefaction to
produce quality-controlled bio-oils;
• To develop bio-liquid upgrading technology such as hydrodeoxygenation and
to scale it up to Process Development Unit (PDU)-scale;
• To study co-processing opportunities of these upgraded bio-oils in archetypal
refinery units such as Fluidized Catalytic Cracking (FCC) and Hydrotreating units on
a laboratory scale;
• To produce discrete oxygenated target chemicals;
• To evaluate the most promising biomass-refinery chain(s) through scenario
analysis based on estimates of the technical, economical and LCA (life-cycle analysis)
performances of the chains.
Coordinator
VTT
PL 1000
FI-02044 VTT
Finland
Contractors involved
VTT
BTG
University of Twente
Shell Global Solutions International
CNRS
Arkema
Metabolic Explorer
INNVENTIA
University of Groningen
Aalto University
Institute of Wood Chemistry – Hamburg/ vTI
National Institute of Chemistry, Slovenia
Boreskov Institute of Catalysis
ALMA Consulting group
Albemarle
CHIMAR
Technical University Eindhoven
Work performed
Research is carried out within six sub-projects (SP). The overall structure of the project is
shown below with a rough outline of material flows from biomass to end products. This also
shows the interaction between the sub-projects.

Figure 1. Project structure
SP1: Improving bio-oil quality and its primary fractionation
Feedstock production for upgrading are developed in SP1 in three subtasks:
- The in-situ filtering of pyrolysis vapours to yield an improved oil with a low ash
content and low alkali metals for further upgrading
- Fractionation of bio oil to three main product streams to allow selective (catalytic)
conversion steps for the fractions in SP2 such as hydrodeoxygenation (HDO),
decarboxylation (DCO) and High Pressure Thermal Treatment (HPTT)
- Production of high-sulphidity hardwood Kraft lignin to be characterized for
liquefaction
In the first task, both temperature and pressure drop were controlled across the hot gas vapor
filter during a two hour run in the laboratory reactor using pine wood as feedstock. However,
the same results could not be achieved for biomasses with a high ash content.
Yields of the filtered oils were comparable to the yields obtained in the experiments using
cyclones only. Integration of the filter in the fluidized bed prevents an increased pyrolysis
vapor residence time as observed with external filtering of pyrolysis oil vapors, thereby
preventing excessive secondary cracking reactions and lowering of the oil yield.
The quality of the filtered oil is better than when cyclones are used: the filtered oil contains
significantly less solids, alkali metals and ash as compared to cyclone oil. There were no
significant differences in elemental composition of the pyrolysis oil produced via the filter
line and cyclone line.
Fractionation of bio oil is developed in the second task. The bio-oil is phase separated into a
water soluble aqueous phase, and a water insoluble lignin bottom phase. After pyrolysis, the
aqueous upper phase was separated from the viscous lignin bottom phase by either letting the
liquid product stand in a measuring flask, or by centrifugation. From the aqueous upper phase
sugar-like compounds were separated from the water and low molecular weight oxygen
compounds by evaporation in vacuum. The purity of the fractions was determined by the
solubility based fractionation scheme.
A higher bio-oil water content improves the phase separation, but at the same time the
recovery of ‘sugars’ and chemicals from the aqueous phase will be more difficult and
expensive due to the high amount of water present. An optimum purity level for the separated
fractions must be defined, before this concept can be verified on a Process Development Unit

(PDU) scale. The lignin and sugar fraction may be upgraded into fuels, while the light volatile
compounds in the aqueous phase may be used for chemicals.
Alternative feeds for the BIOCOUP chain are developed in the third subtask. Laboratory
softwood and hardwood Kraft cooking at high (80%) and normal (35%) sulphidity has been
performed. The softwood and hardwood lignins have been isolated from the Kraft cooks.
After isolation all lignin samples are characterised with respect to chemical composition, ash
content and thermal properties .
SP2: Develop smart upgrading strategies of pyrolysis oils to enable co-processing
Three strategies have been studied for the upgrading of pyrolysis oils. These are
hydrodeoxygenation (HDO), High Pressure Thermal Treatment (HPTT) and decarboxylation
(DCO). In HDO, pyrolysis oil is stabilized with hydrogen and this upgrading route has been
found to be more promising than HPTT and DCO.
SP3 has shown that deep deoxygenation of pyrolysis oil is not necessary for the successful coprocessing
of upgraded pyrolysis oil in lab scale FCC and hydrotreating units: oxygen levels
up to 30% can be allowed. During pyrolysis oil upgrading, the stabilization of pyrolysis oil is
thought to be more important than (deep) deoxygenation.
HDO oil samples were produced using a wide variety of catalysts and process conditions.
Process insight using model components, pyrolysis oil fractions and whole pyrolysis oil has
helped in developing strategies to minimize hydrogen consumption and reaction times.
Several new catalysts with good performance have been developed and tested. Suggestions
for the definition of HDO oil quality with respect to co-processing have been made.
It has been established that HPTT oil is not suitable for either further upgrading by HDO or
direct processing in lab scale refinery units (plugging, miscibility problems with typical
refinery feed). The polymerization behavior in HPTT processing has been studied as a
function of process conditions. Several strategies to suppress polymerization/char formation
during HPTT have been suggested, which also help in developing process concepts to
suppress polymerization in HDO. Work on HPTT was stopped at M48. Experimental results
on DCO so far show large similarities with HPTT: a strong polymerization and an oil product
not suitable for co-processing.
Work on DCO was stopped at M48.
A PDU has been designed and constructed to be able to produce sufficient quantities ( > 5 L)
of HDO oil for pilot testing in refinery processes in SP3.
SP3: Co-processing of upgraded bio-oils in archetypal refinery units
In this sub-project, there are two complementary activities: i) fundamental understanding is
gained from closely studying the reactivity of these bio-oils and model compounds ii) the
evaluation of these bio-oils in lab scale refinery units.
The impact on the hydrodesulpurisation performance has been studied by i) the addition of
these bio-oils ii) reaction temperature iii) hydrogenation catalyst. Possible degradation
compounds have been identified which may be involved in a loss of efficiency of the HDS
process. Insight into the mechanism of converswion has been gained by examining the origin
of the coke formation. In addition, use of the analytical technique Size Exclusion
Chromatography allows better identification of the fate of the higher molecular weight part of
the bio-oil.

In parallel with the above activities, the upgraded bio-oils from SP2 have been extensively
evaluated in lab scale Fluidised Catalytic Cracking or continuous hydrotreating units. In
coprocessing these upgraded bio-oils with representative standard FCC feeds such as a
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. Continuous
hydrotreating of the upgraded pyrolysis oil is technically feasible and affords a aromatic
diesel-like bio-components. This suggests that the co-processing of upgraded bio-oils with
FCC feeds using standard FCC conditions and catalysts can afford bio-hydrocarbons from a
lignocellulosic feed source.
SP4: Selective separation of discrete target oxygenates
At M36 the extraction based isolation technologies and the distillation based fractionation
technologies for aldehydes, phenolics and acids have been optimized. The main technology
objective for the M37-M48 period was the establishment of detailed models and exprimental
data on the optimized isolation and fractionation technologies required for the conceptual
process designs and economical feasibility evaluations. This work has been completed and by
the start of the last project year the required models and experimental data conducted have
been established for all isolation and fractionation technologies
Using the optimized technologies optimal fractions glycoaldehyde, phenolics and acid acid
loaded extractant were produced and delivered to the SP4 partners. These fractions were used
in combination with some earlier produced optimized fractions for chemicals/product
synthesis and performance evaluation. The improved aldehyde fraction and phenolics fraction
has been evaluated in wood panels. The results showed that the aldehyde fraction increases
the shear strength of the wood panels. The improved phenolics fraction allowed for slightly
higher substitution of chemical phenolics. More detailed product evaluations of bioliquid
based adhesives have demonstrated a general improvement of adhesive properties of bioliquid
derived adhesives over chemical derived adhesives. The feasibility of biochemical reduction
of bioliquid derived glycoaldehyde into ethylene glycol has been demonstrated as well as the
production of bioliquid derived acetic acid.
SP5: Scenario analysis
A techno-economic analysis of the base production chain as well as two variants of the
BIOCOUP concept has been assessed and compared to an earlier reference chain, which was
based entirely on state-of-the-art literature knowledge.
Compared to the reference case assessed previously, the base concept has the following new
features, which have been experimentally developed within the project:
- Hydrodeoxygenation (HDO) of bio oil
- Recovery of chemicals from the aqueous phase from the HDO (at the time of reporting not
fully developed)
- Co-upgrading of the HDO oil in a refinery Fluid Catalytic Cracker (FCC)
HDO carried out at 340 ºC is the most competitive concept, in which a relatively low
proportion of chemicals is produced. HDO at 230 ºC is the least competitive; the reference
case lies between these two alternatives. When the amount of chemicals is increased, the
competitiveness of the HDO340 is slightly improved. The competitiveness of the HDO230
improves considerably when the value and amount chemicals are increased.

None of the alternatives are competitive with conventional fuels at current prices. The
reference case becomes the most competitive of the chains compared, when the price of
gasoline is 1.5 times above current prices. Both the reference case and HDO340 have a
positive net present value, when the price of gasoline is 1.7 times higher than now.
SP6: Transversal activities
The SP6 activities run for the entire project and they aim to facilitate the achievement of the
project objectives. Dissemination is ongoing with an increasing number of conference
presentations and publications being submitted to peer-reviewed journals. A BIOCOUP
workshop also took place in Helsinki at the second Nordic wood biorefinery conference.
Details of these activities can be found on the BIOCOUP website www.biocoup.eu.
A watch is being kept on standardisation activities, to raise the awareness of standards
organisations and other relevant networks and associations on both the activity within
BIOCOUP and how this can contribute to the development of existing or new standards and
work practices.
Training activities organised by BIOCOUP have included two 1-week long courses held at
M11 and M35 and organised by Aalto (then acting as TKK). These were very successful with
lectures and attendees from both industry and universities. Training is also on-going within
the consortium so that the understanding of the many aspects associated with the biorefinery
concept can be developed.
The project management activities remain essential for managing this large Integrated Project
with 17 partners and ensuring that the resources are used most effectively.