(279g) Accelerated Catalytic Processing of Fossil and Biorenewable Feedstocks Using Avantium's Technology and Methodologies

Accelerated
catalytic processing of fossil and biorenewable feedstocks using Avantium's Technology
and methodologies

Pieter Imhof and
Alex Pérez de Santana

Avantium

Zekeringstraat 29, 1014 BV, Amsterdam, The Netherlands )

Introduction

Worldwide specifications for transportation fuels have
become more stringent over the years. This has fueled catalyst development in
the field of fossil and biorenewable feedstocks. Avantium's methodologies
and proprietary fixed bed technology, which is used in Avantium's catalyst
research services and in the Flowrence^TM, allows our customers to
accelerate their catalyst and process development. Being able simultaneously
study various process steps as well as to test 16-64 catalysts in parallel reduces
the time to develop a new catalyst generation and find the most economical
process from multiple years to less than a year. Avantium's
capabilities allow testing of both extrudates and sieved materials with a
discrimination power similar to those normally only observed in pilot test
units. Testing both extrudates and sieved materials creates the opportunity to
effectively evaluate effect of mass transport limitation and catalyst shape.

The unique capabilities of Avantium's
methodologies and technology will be reviewed using real data from hydroprocessing/cracking, Fischer Tropsh
and the selective hydrogenation of 5-ethoxymethylfurfural case studies. The
accelerated methodologies used by simultaneously researching various steps
towards the development of a new process and catalyst will be presented. Additionally
the data obtained from Avantium's technology will be compared
to those obtained in a pilot plant using same feed and same process conditions.
Moreover, the test results of extrudates and sieved material for different
catalyst systems in ULDS, VGO hydrocracking studies will
be compared.

Experimental

Avantium's gas and trickle flow technology
is applied for ULSD, VGO-HDS, hydrocracking, Fischer Tropsch and a selective hydrogenation reaction. Testing
consists of 4 reactor blocks with 4-16 reactors each. The units are equipped
with controllers allowing accurate feeding of hydrogen and diesel, SRGO and VGO
feeds. The unit is operating fully automated 24/7. When required the liquid
samples are collected using a 4x16 sample robot makes it possible to sample for
multiple days without operator interference. The catalyst volume applied for
the test in the unit is between 0.5-1ml. Both sieved materials and complete extrudates
have been loaded and tested. In the ULSD, VGO-HDS study extrudates and sieved
material of respectively 1.6 mm and 200-400micron have been applied.

In the selective hydrogenation of
5-Ethoxymethylfurfural case study, 48 catalysts under a variety of conditions
were tested. The major observed reaction pathways are outlined in  REF _Ref292086866 \h Scheme
1.The results show that both substrate conversion
and product selectivity are sensitive towards temperature changes and solvent
effects. The best results of >99% yield to the desired product, 5-

ethoxymethylfurfuryl
alcohol, are obtained using an iridium/chromium (Ir/Cr)
catalyst. In the ULDS/VGO case study two commercial catalysts have been tested
in both Flowrence^TM unit and pilot plant.
In the Flowrence^TM unit 4 reactors are
loaded with extrudates of Cat A, 4 reactors are loaded with sieved material of
Cat A, 4 reactors with extrudates of Cat B and 4 reactors with sieved material
of Cat B. In the case of the pilot plant only extrudates have been applied.
Catalysts are tested at 80 bar, H2/Oil ratio of 800 and low LHSV at 355, 365,
375 and 385 °C. Both sulfur and nitrogen content of the treated VGO have been
analyzed on a daily basis.

Scheme  SEQ Scheme \* ARABIC 1
Hydrogenation pathways for the catalystic
hydrogenation of 5-ethoxymethyl furfural

In the Fischer Tropsch case
study, using 64 reactors in parallel for over a period of 3 months
uninterrupted, catalysts are compared to one another while accurately being
able to combine the online analysis with offline analysis for determining the
alpha values (Anderson Schulz Flory distribution).

Results and
Discussion

In  REF _Ref292086417 \h Figure 1 the performance of
catalyst A and B in the Flowrence unit and in the
pilot plant are shown for the desulfurization of a VGO feed. As can be seen
from figure1 the ranking and behavior of both catalysts are very similar in the
Flowrence^TM unit and pilot plant. For the
HDS performance slightly lower sulfur concentrations are found than in the
pilot plant.

The small differences in performance between the Flowrence^TM and pilot plant are due to small
differences in actual reactor temperature (isothermal vs. adiabatic), better
plug flow in the Flowrence unit and small difference in hydrodynamics.

The accuracy of the Flowrence test data allows discrimination between catalysts
that show only 2-3°C difference in temperature required to achieve a certain
activity.

Similar data demonstrating the performance of Flowrence technology for HDN and hydrocracking
is also presented.

Figure
 SEQ Figure \*
ARABIC 1 Comparison Sulfur data from Flowrence^TM
unit with those obtained in Pilot plant.

Please
see  REF _Ref292087257 \h Figure
2 for one of the various summary
of the selective hydrogenation results. All hydrogenation reactions were
performed in trickle-flow using a 16-parallel flow reactor set-up. The results show
that both substrate conversion and product selectivity are sensitive towards temperature
changes and solvent effects. The best results of >99% yield to the desired
product, 5- ethoxymethylfurfuryl alcohol, are
obtained using an iridium/chromium (Ir/Cr) catalyst.

Figure
 SEQ Figure \*
ARABIC 2 Semilogarithmic plot of the ratio between the selectivities
towards the unsaturated alcohol 2 and its the diethyl
ether 5 as a function of conversion at three temperatures. 

In  REF _Ref292087308 \h Figure 3 the stability of the Avantium reactor technology is demonstrated by means of the
CO conversion over a 3 month period in Fischer-Tropsch
synthesis. Accuracy of the data from campaign to campaign as well as Avantium catalyst synthesis reproducibility will be demonstrated.

Figure  SEQ Figure \* ARABIC 3 CO
conversion for a number of different catalysts in Fischer-Tropsch
synthesis during a 3-month test.

Conclusions

Avantium's methodologies and
technologies are very powerful acceleration tools to speed up catalyst and
process development efforts in the field of fossil and biorenewble
feedstocks.

The data presented show that data obtained in Avantium technology relate very well to those obtained in a
pilot unit and demonstrate the application flexibility and data accuracy that Avantium can be achieved today.