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.

    Flowrence® products specifications

    Reactor Section

    Easy and quick reactor exchange system. Possibility to use quartz reactors at high pressure.

    1 block of 4 reactors

    HT = High Temperature max. 800°C nominal, limited to 925°C (<0.5°C reactor to reactor deviation)

    4 blocks of 4 reactors

    HT  or MT = Medium Temperature max. 525°C (<0.5°C block-to-block deviation)

    16 reactors with iRTC

    individual Reactor Temperature Control
    max. 550°C (<0.5°C reactor-to-reactor)

    4 reactors with iRTC

    individual Reactor Temperature Control
    max. 550°C (<0.5°C reactor-to-reactor)

    Temperature Ranges (°C)

    100 – 800°C
    up 925°C (Option)

    50 – 525°C
    100 – 800°C
    up 925°C (Option)

    50 – 550°C

    50 – 550°C

    Reactor Types

    L= Length
    OD= Outer Diameter
    ID= Inner Diameter
    SS= Stainless Steel (< 550⁰C)
    Qz= Quartz (< 925⁰C)

    L 300 mm 561 mm
    OD 3 mm 6 mm
    ID SS 2 / 2.6 mm 2 / 3 / 4 / 5 mm
    ID Qz 2 mm 2 / 4 mm
    300 mm 561 mm 561 mm
    3 mm 3 mm 6 mm
    2 / 2.6 mm 2 / 2.6 mm 2 / 3 / 4 / 5 mm
    2 mm 2 mm 2 / 4 mm
    561 mm
    3 mm
    2 / 2.6 mm
    2 mm
    561 mm
    3 mm
    2 / 2.6 mm
    2 mm

    Maximum Catalyst Bed Length

    (isothermal zone tolerance ± 1°C)
    Note: isothermal length is dependent on the temperature range

    300 / 3 HT 561 / 6 HT
    >120 mm @ 450°C >200 mm @ 500°C
    >90 mm @ 800°C >150 mm @ 800°C
    >140 mm @ 925°C
    300 / 3 HT 561 / 3 MT 561 / 6 HT
    >120 mm @ 450°C >310 mm @ 450°C >200 mm @ 500°C
    >90 mm @ 800°C >150 mm @ 800°C
    >140 mm @ 925°C
    561 / 3 MT iRTC
    250°C ±0.5°C 41cm (4reactors)
    350°C±0.5°C 38cm (4reactors)
    550°C±0.5°C 28cm (4reactors)
    3 reactors at 550°C, 1 reactor 350°C:
    550°C=27cm 350°C=41cm ±0.5°C
    561 / 3 MT iRTC
    250°C ±0.5°C 41cm (4reactors)
    350°C±0.5°C 38cm (4reactors)
    550°C±0.5°C 28cm (4reactors)
    3 reactors at 550°C, 1 reactor 350°C:
    550°C=27cm 350°C=41cm ±0.5°C

    Catalyst Volume (mL)

    (isothermal zone)

    0.2 - 0.6 mL 0.4 - 2.0 mL
    0.2 - 0.6 mL 0.4 - 1.0 mL 0.4 - 2.0 mL
    0.4 - 1.0 mL
    0.4 - 1.0 mL

    Pressure Ranges (barg)

    2 – 80 barg
    0.5 – 180 barg (option)

    2 – 100 barg
    0.5 – 180 barg

    2 – 80 barg
    0.5 – 180 barg

    2 – 20 barg
    2 – 50 barg (option)

    Reactor Pressure Control

    Advanced control RSD ±0.1 barg at reference conditions (gas phase only and 20 barg). For trickle flow Advanced control RSD ±0.5barg.

    Standard (±0.5 barg)
    Advanced (±0.1 barg) (option)

    Standard (±0.5 barg)
    Advanced (±0.1 barg) (option)

    Advanced (±0.1 barg)

    Advanced (±0.1 barg)

    Gas Feed Lines

    (#Gas Feeds)

    Up to 6 + Diluent gas

    He, Ar, N2, H2, CH4, CO2, C2H4, C2H6, O2/Inert (≤5%), CO, Other gases

    Up to 7 + Diluent gas

    He, Ar, N2, H2, CH4, CO2, C2H4, C2H6, O2/Inert (≤5%), CO, Other gases

    Up to 7 + Diluent gas

    He, Ar, N2, H2, CH4, CO2, C2H4, C2H6, O2/Inert (≤5%), CO, Other gases

    Up to 6 + Diluent gas

    He, Ar, N2, H2, CH4, CO2, C2H4, C2H6, O2/Inert (≤5%), CO, Other gases

    Online Analysis

    Full integration GC, MS , GC/MS with data visualisation (option)

    Full integration GC, MS , GC/MS with data visualisation

    Full integration GC, MS , GC/MS with data visualisation

    Full integration GC, MS , GC/MS with data visualisation

    Liquid Feed

     Split feeding 8 + 8 reators (option)

    Pump-Coriolis dosing system
    (ambient, cooled)

    Pump-Coriolis dosing system
    (ambient, cooled, heated 80°C)

    Pump-Coriolis dosing system
    (ambient, cooled, heated 80°C)

    Pump-Coriolis dosing system
    (ambient, cooled, heated 80°C)

    Liquid Distribution

    Microfluidic Distribution
    (4-channel glass-chip)

    Microfluidics Distribution
    (4x4-channel glass-chip)
    (16-channel glass-chip)
    Active Liquid Distribution (option)
    (with automatic isolation valves)

    Active Liquid Distribution
    (with automatic isolation valves)

    Microfluidic Distribution
    (4-channel glass-chip)

    Liquid Sampling

    (G/L Separation)

    Parallel liquid sampling (4 x 20ml vials) with sequential on-line gas phase sampling (option)

    Automated liquid sampling (4 rows x 16 vials x 8ml) with sequential on-line gas phase sampling (option)

    Automated liquid sampling (4 rows x 16 vials x 8ml) with sequential on-line gas phase sampling (option)

    Parallel liquid sampling (4 x 20ml vials) with sequential on-line gas phase sampling (option)

    Reactors Effluent Handling

    (Off-line Analysis Connection)

    Full heated circuit up to 180°C with sequential on-line full gas phase sampling (option)

    Full heated circuit up to 200°C with sequential on-line full gas phase sampling

    Full heated circuit up to 200°C with sequential on-line full gas phase sampling

    Full heated circuit up to 200°C with sequential on-line full gas phase sampling

    Offline Analysis

    Integrated Workflow: SimDist, total S/N, liquid density, balance, label printer, barcode (option)

    Integrated Workflow: SimDist, total S/N, liquid density, balance, label printer, barcode

    Integrated Workflow: SimDist, total S/N, liquid density, balance, label printer, barcode

    Integrated Workflow: SimDist, total S/N, liquid density, balance, label printer, barcode

    Waste Handling

    Ambient temperature
    Heated wax trapping (option)

    Ambient temperature / Cooled containers / Heated compartment (wax trapping, heavies)

    Ambient temperature / Cooled containers / Heated compartment (wax trapping, heavies)

    Ambient temperature / Cooled containers / Heated compartment (wax trapping, heavies)

    Safety

    Gas sensors and control box (CO, LEL, VOC)

    Gas sensors and control box (CO, LEL, VOC)

    Gas sensors and control box (CO, LEL, VOC)

    Gas sensors and control box (CO, LEL, VOC)

    Flowrence® Software

    Flowrence® recipe builder, control & database builder

    Flowrence® recipe builder, control & database builder

    Flowrence® recipe builder, control & database builder

    Flowrence® recipe builder, control & database builder

    Microfluidics modular gas distribution

    Unrivalled accuracy in gas distribution with patented glass-chips for 4 and 16 reactors, with a guaranteed flow distribution of 0.5% RSD. Quick exchange of glass-chips for different operating conditions. Flexibility to cover a wide range of applications.

    TinyPressure glass-chip holder with integrated pressure measurement

    Compact modular design for gas and liquid distribution. No high-temperature pressure sensors required. Quick exchange of the microfluidic glass-chips, without the need for time-consuming leak testing.

    Tube-in-tube reactor technology with effluent dilution

    Unique tube-in-tube design with easy and rapid exchange of the reactor tubes (within minutes!). No need for any connections. Use of inert diluent gas (outside of reactor) to maintain the pressure prevents dead volumes and back flow. Possibility to use quartz reactors at high pressure applications.

    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. Eliminates the use of high pressure valves.

    Reactor Pressure Control (RPC)

    The most accurate and stable pressure regulator for a 16-parallel reactors with just ±0.1bar RSD. The RPC uses microfluidics technology to regulate the pressure of each reactor, maintaining equal distribution of the inlet flow over the 16 reactors.

    Auto-calibrating liquid feed distribution, measurement, and control

    Distribution of difficult feedstocks e.g., VGO, HVGO, DAO. Liquid distribution 0.2% RSD, making it the most accurate liquid distribution device on the market. Option to selectively isolate each reactor.

    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 avoiding maldistribution, eliminating channeling and incomplete wetting.

    EasyLoad®

    Unique reactor closing system with no connections. Rapid reactor replacement minimizing delays, improving uptime and reliability. Stable evaporation by liquid injection into reactor.

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    Avantium Headquarters

    +31 (0)20 586 8080

    Zekeringstraat 29
    1014 BV Amsterdam
    The Netherlands

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