Representative Pilot Plant Testing of Hydrocracking Catalysts

Hydrocracking is a petrochemical process that converts a heavy oil fraction, typically obtained from crude oil fractionation into lighter fractions e.g. naphtha, kerosene, diesel or jet fuel, by means of a catalyst and hydrogen at higher pressure/temperature. Testing catalysts early in the development phase at real conditions allows a faster way to the market. 

A hydrocracking catalyst contains a zeolitic component for cracking the hydrocarbons , a metal component for the hydrogenation/dehydrogenation and a binder for the physical stability. Commercially Zeolite Y  or Zeolite Beta are applied in combination with Nickel/Tungsten/Molybdenum as metals and Alumina as a binder. 

There a several catalysts suppliers for hydrocracking catalysts (e.g. Shell, UOP, Axens, Chevron-Lummus, Haldor Topsoe) which develop new catalysts with increased activity, higher selectivities to match the market demands of the various regions, and process heavier feeds.

In recent years, there has been a clear trend towards small laboratory reactors. Parallel testing allows for replication – determination of statistical significance of results obtained – and for simply evaluating more catalyst options side-by-side at the same time. In addition, smaller volumes will reduce the amount of feed required avoiding the typical issues associated with obtaining large quantities like handling, shipping and storage (for longer term availability of reference feed material).

High-Throughput Catalyst testing – Your chance to increase the success

Accurate catalyst evaluation is an important step in optimizing catalytic processes with respect to product yield, energy efficiency and overall product quality. Historically, the performance of heterogeneous catalysts is evaluated using large reactor systems which typically vary between 20 to 300 ml.

Reactors of smaller scale are usually more ideal in terms of heat flow and hydrodynamics compared to larger reactors and therefore provide data that is intrinsically easier to translate to a larger (industrial) operating scale. In additon, a broader parameter space of catalyst can be evaluated which increases the chance of success significantly.

Small scale parallel fixed bed reactor systems designed for catalyst intake up to 1 ml, have been developed at Avantium in order to enhance catalyst development and selection for refinery applications.

Catalyst suppliers own and use several of our Flowrence® small scale systems to maintain a continuous effort in catalyst development and stay ahead of their competitors in an ever-changing landscape of refinery operations.

High-Throughput Catalyst testing – Your chance to increase the success

Accurate catalyst evaluation is an important step in optimizing catalytic processes with respect to product yield, energy efficiency and overall product quality. Historically, the performance of heterogeneous catalysts is evaluated using large reactor systems which typically vary between 20 to 300 ml.

Reactors of smaller scale are usually more ideal in terms of heat flow and hydrodynamics compared to larger reactors and therefore provide data that is intrinsically easier to translate to a larger (industrial) operating scale. In additon, a broader parameter space of catalyst can be evaluated which increases the chance of success significantly.

Small scale parallel fixed bed reactor systems designed for catalyst intake up to 1 ml, have been developed at Avantium in order to enhance catalyst development and selection for refinery applications.

Catalyst suppliers own and use several of our Flowrence® small scale systems to maintain a continuous effort in catalyst development and stay ahead of their competitors in an ever-changing landscape of refinery operations.

Flowrence® technology delivers results comparable to  20 ml bench scale

 The performance and reproducibility of 6 hydrocracking catalysts were tested in the Flowrence® micro-pilot plant under commercial conditions using 16 parallel reactors. These 6 different catalysts were loaded in duplicates and triplicates in order to test reproducibility and obtain absolute performance data.

The catalysts were loaded in the presence of diluent particles in order to avoid catalyst bypassing and to ensure plug flow conditions as described here. Hydrocracking of a doped VGO (60% above 600°Fwas carried out under commercial conditions [ 650-850°F; 150 bar; LHSV = 0.5-4 h-1; Gas/Oil 300-1500; Catalyst loading = 0.6 ml (whole extrudates) ].

The comparison of the results obtained in the Flowrence® 0.6 ml scale with the 20 ml bench scale showed the same catalyst ranking and very similar absolute conversion and selectivity levels, with ±1.5% Mass balance at 15-95% Conversion, a ± 2°F Reactor-to-reactor reproducibility and ±0.5% Total distillate mass yield when data compared at the same conversion.

    Fig. 1. Trequired – Toffset (°F) to reach 65% conversion, 20 ml reactor vs Flowrence®.

    Conclusions

    • The Flowrence® reactor systems operating with catalyst volumes of 0.5-1.0 ml have a proven scalability for larger scale reactors, in both catalyst ranking and absolute values of activity and yield trends.
    • Scalability; the results obtained in our small-scale reactor testing system for hydrocracking showed a good relation with measurements obtained in 20 ml bench scale unit from a major vendor.
    • Reproducibility; as the catalyst packing in our small-scale reactor is straightforward, and does not require any special procedures, excellent reactor-to-reactor repeatability is obtained. This is demonstrated by a <2°F deviation between duplicate reactors for the temperature required to achieve a target conversion.
    Fig. 2. Total distillate yield Y-Yoffset (%) at 65% conversion, 20 ml reactor vs Flowrence®
    Fig. 2. Total distillate yield Y-Yoffset (%) at 65% conversion, 20 ml reactor vs Flowrence®

    Conclusions

    • The Flowrence® reactor systems operating with catalyst volumes of 0.5-1.0 ml have a proven scalability for larger scale reactors, in both catalyst ranking and absolute values of activity and yield trends.
    • Scalability; the results obtained in our small-scale reactor testing system for hydrocracking showed a good relation with measurements obtained in 20 ml bench scale unit from a major vendor.
    • Reproducibility; as the catalyst packing in our small-scale reactor is straightforward, and does not require any special procedures, excellent reactor-to-reactor repeatability is obtained. This is demonstrated by a <2°F deviation between duplicate reactors for the temperature required to achieve a target conversion.

    Single-Pellet-String-Reactors (SPSR)

    No dead-zones, no bed packing & distribution effects. The catalyst packing is straightforward and does not require special procedures. A single string of catalyst particles is loaded in the reactors with an internal diameter (ID) that closely matches the particle average diameter. This applies to single catalyst systems, as well as stacked-bed systems. The use of a narrow reactor avoids any maldistribution of gas and liquid over the catalyst bed, thereby eliminating catalyst-bed channeling and incomplete wetting of the catalyst.

    The most accurate and stable pressure regulator for 16-parallel reactors

    The most accurate and stable pressure regulator for a multi-parallel reactors with just ±0.1bar RSD at reference conditions. The Reactor Pressure Controller (RPC) uses microfluidics technology to individually regulate the back-pressure of each reactor. By measuring the inlet pressure of each reactor, the RPC maintains a constant inlet pressure by regulating the backpressure. As a result, the distribution of the inlet flows over the 16 reactors is unaffected and a low reactor-to-reactor flow variability is achieved.

    Reactor pressure control is not only important to ensure accurate pressure control, but also to help maintaining equal distribution of the inlet flow over the 16 reactors.

    Automated liquid sampling system

    Programmable, fully automated liquid product sampling robot for 24/7 hands-off operation. Robot equipped with a compact manifold aiming at depressurizing the effluent immediately after each reactor to atmospheric pressure. Reactor effluent is depressurized by a miniaturized (low volume) parallel dome regulator, allowing a stable control of gas or gas/liquid product streams. This eliminates the use of valves at high pressure (such as multi-position valves), which are prone to leakage.

    Gas liquid separation is sone directly by collecting the liquid products in sample vials and directing the gas products to the online gas analyzer. This approach minimizes required flushing times in the downstream section of the reactor eliminating the need for high pressure gas-liquid separators, level sensors, and drain valves.

    EasyLoad® reactor closing system

    Unique reactor closing system, no connections required. With a rapid reactor replacement minimizing delays, improving uptime and reliability. Sealing of up to 16 reactors by simply closing the ‘top-box’ in a single action. No leak testing required!

    Stable evaporation by liquid injection into reactor

    The direct injection of liquid into the top of the reactor and the consecutive conditioning zone allows feeding of broad range of liquids and concentrations. Various types of liquids, both aqueous and oil phase are successfully evaporated and fed to the reactors.

    Tube-in-tube reactor technology with effluent dilution

    This unique tube-in-tube feature allows an easy and rapid exchange of the reactor tubes (within minutes!) with a single o-ring at the top of the reactor without the need for any connections. The use of an inert diluent gas (outside of reactor) to maintain the pressure stops undesirable reactions immediately after the catalyst bed while serving as a carrier gas to the GC, facilitating the analysis of high boiling point components, preventing dead volumes and back flow, and reducing the time required to transfer gas and liquid effluent products to the analytical instruments.

    The tube-in-tube design enables the use of quartz reactors at high pressure applications.

    Compact TinyPressure module glass-chip holder with integrated pressure measurement

    Holds the microfluidic glass-chips for gas distribution and measures inlet (and outlet) pressure of the 16 parallel reactors at ambient temperature, allowing online measurement of catalyst bed pressure drop.

    No high-temperature pressure sensors required. Pressure range of 10 – 200 bar (high pressure) or 0.5 – 10 bar (low pressure).

    The modular design enables easy calibration and quick exchange of the microfluidic glass-chip, without the need for time-consuming leak testing.

    Microfluidics modular gas distribution

    Unrivalled accuracy in gas distribution with patented glass-chips for 4 and 16 reactors, tested with a guaranteed flow distribution of 0.5% RSD channel-to-channel variability. Quick exchange for different operating conditions, offering the unique flexibility to cover a wide range of applications using the same reactor system.

    Auto-calibrating liquid feed distribution, measurement, and control

    The most accurate liquid distribution for high throughput systems with real-time liquid flow measurement and control for 16-parallel reactors. Auto-calibrating function enabled by a single flow sensor guarantees that all 16 reactors are continuously operated at the desired LHSV, all the time. Innovative design based on our microfluidic glass-chips with integrated temperature-control. The system continuously regulates the liquid distribution to all 16 reactors, and together with our Reactor Pressure Control technology, eliminates the impacts of pressure variations in the flow distribution.

    Proven technology with difficult feedstocks with high viscosity, such as VGO, HVGO and DAO: no blockage and or breakage observed. Different glass-chips available for different viscosities.

    Liquid distribution errors below 0.2% RSD, making it the most accurate parallel liquid flow distribution device on the market.

    Option to selectively isolate the liquid flow to any of the 16-parallel reactors.

     

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