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 Chemicals BV

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 08D0C9EA79F9BACE118C8200AA004BA90B02000000080000000E0000005F005200650066003200390032003000380036003800360036000000 .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 08D0C9EA79F9BACE118C8200AA004BA90B02000000080000000E0000005F005200650066003200390032003000380036003400310037000000 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 08D0C9EA79F9BACE118C8200AA004BA90B02000000080000000E0000005F005200650066003200390032003000380037003200350037000000 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 08D0C9EA79F9BACE118C8200AA004BA90B02000000080000000E0000005F005200650066003200390032003000380037003300300038000000 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.