Hydrogenation processes, distillation and catalyst tests

Upgrading of oils and gases from regenerative feedstocks

Fraunhofer UMSICHT Sulzbach-Rosenberg has been involved in the research of (bio)refinery processes for years. The goal is the production of sustainable liquid energy sources (e.g. latest generation biofuels) for mobility and storage, as well as the production of defossilized chemicals and basic materials for the chemical industry.

Research and development activities focus on the development and optimization of downstream process routes for petroleum substitutes, e.g. pyrolysis oils, synthesis gases, halogenated hydrocarbons or Fischer-Tropsch products. One focus is on the removal of heteroatoms.

Range of services: downstream processes

Our range of services includes:

Testing and optimization of catalysts on a pilot plant scale
Catalytic conversion of reactants into specific products - from laboratory to pilot plant scale
Distillative separation of intermediates
Design of efficient process routes, including reaction control, reactor design and process simulation
Continuous hydrotreatment (up to 3 liters of oil / liquid feedstock per hour) in pilot-scale reactor

Thanks to test rigs and experimental reactors in different sizes, we can offer the right setup for each project, e.g. prescreening trials in a batch reactor, followed by continuous hydrogenation (hydrotreatment) at larger scale and subsequent scale-up to pilot scale.

Overview Services in Downstream Processing

The Fraunhofer UMSICHT Sulzbach-Rosenberg branch develops, optimizes and evaluates downstream processes for liquid and gaseous feedstocks.

Catalyst tests

We offer various options for the research and optimization of catalysts: from tests and adaptation to new feedstocks to complete, feedstock-specific new development.

The catalyst material can be provided or we can produce it ourselves on a laboratory or pilot plant scale. Likewise, the feedstock can be provided and experiments can be carried out with the corresponding specifications.

On the one hand, liquid reactants such as pyrolysis oils, halogen-containing hydrocarbons, Fischer-Tropsch products or other liquid feedstocks can be tested. On the other hand, it is possible to test gaseous feedstocks such as synthesis gas or waste gas streams from industrial processes in different compositions, to provide them with potential catalyst poisons, and to test the reaction behavior.

For catalyst research and optimization, we evaluate activity, selectivity, productivity and aging of catalysts. In order to obtain meaningful test results, we develop an individual test program with the necessary analytics. This is very diverse and ranges from GCxMS, elemental analysis, TAN, water content, calorific value, etc. to the analysis of catalysts using XRD, SEM, EDX.

Distillations

We perform batch distillations with volumes per batch between 2 and 18 liters. Larger volumes can be processed in several batches.

Here, overhead products can be distilled up to a boiling temperature of up to 350 °C under atmospheric pressure. This temperature can be further increased by distillation under vacuum. The distillations take place under an inert atmosphere.

All parameters during distillation are logged so that precisely documented results are available at the end of a test series.

The exact execution of the distillation and the required analyses are planned together. Simulations of the distillations can also be carried out for this purpose.

Catalytic conversion / hydrotreatment of various feedstocks

We perform catalytic conversions such as hydrogenations (hydrotreatment), isomerizations, reformations and other catalytic conversions of various feedstocks.

Technical equipment

Catalyst test stand / laboratory hydrogenation

Combined batch and continuous catalyst test rig for heterogeneous catalysis between gas and solid. Batch reactor for screening catalysts and liquid or gaseous feedstocks and continuous laboratory test rig for transferring conditions from discontinuous to continuous operation.

Katalysator-Teststand Labor — © Fraunhofer UMSICHT
Laboratory scale catalyst test rig

Up to 10 g catalyst possible
Flow rates from up to 4 Nl/min
Available gases: H2, CO, CO2, He, N2 + one other mixed test gas.
Pressure: 100 bar
Temperature: up to 330°C (thermal oil heating)

Batch hydrogenation on a laboratory scale up to 50ml

Hydrogenation of approx. 30ml pyrolysis oil

Screening of catalysts (checking catalyst performance for pyrolysis oil)
Reactor electrically heated up to 450°C
Pressures up to 150 bar
Gas flows with H2 and N2

Continuous hydrogenation plant / Hydrotreatment

Pilot-scale hydrogenation system with three hydrogenation reactors that can be interconnected in different configurations. Production of larger quantities of product and testing of larger quantities of catalyst.

Picture Continuous hydrogenation plant — © Fraunhofer UMSICHT
Continuous hydrogenation plant with 3 reactors

Fig. 2 Continuous hydrogenation plant — © Fraunhofer UMSICHT
Integrated gas recycling and GC online analysis

Fig. 3 Continuous hydrogenation plant — © Fraunhofer UMSICHT
Throughput of 3 kg/h feedstock, 8000 l/h water feedstock

The plant consists of three pressure reactors, which can be operated in series or parallel, depending on the application. The volume of the three reactors is 2.5 liters each and they can be filled with the catalyst depending on the dilution and bulk density of the catalyst.

The plant operation is technically certified up to 500°C and 200 bar. The pressure reactors can hold a total volume of 7.5 liters of catalyst. Recycling of the process gases is possible to increase the efficiency of the overall process.

With regard to the catalysts used, the hydrogenation plant shows maximum flexibility. A wide variety of shaped bodies as well as sintered supported catalysts can be used. Activation of the catalysts in the pressure reactors with a wide variety of activation reagents can be carried out, thus enabling activation of the catalysts by sulfidation reactions by converting the catalyst from the oxidic form to the sulfide form. Reagents such as dimethyl disulfide and hydrogen can be used for this purpose to provide the hydrogen sulfide. Catalysts can also be converted to the active form only by reduction with hydrogen.

Analytically, the hydrogenation conversion is investigated using an online GC FID/WLD instrument. Permanent gases such as H₂, CO, CO₂ and N2 can be analyzed. The online GC is also calibrated for the products of hydrogenation. The products include H2S, NH3 and H2O, but also by-products of hydrogenation, which are formed by cracking hydrocarbons.

The calibration of the individual products ranges from 1000 ppm to several percent by volume, depending on the expected quantities.

30 ml sample volume
500 ml reactor volume
Discontinuous operation
Pressure: 200 bar
Temperature: up to 500 °C (electrically heated)
Available gases: Hydrogen and nitrogen

Batch distillation

Maximum operating temperature (sump): 350°C
Evaporator type: round bottom flask 20 liters
Working pressure: 1000 - 1mbar abs.
Column diameter: DN 50
Column length: 1 segment, approx. 1000 mm separation length
Separation capacity with WIRE MESH: up to 25 theoretical plates
Collection vessel: 5000 ml temperature controlled, with drain cock for discharge into Schott laboratory bottles, discharge of individual fractions also possible under vacuum
Batch rectification
flask volume: 20 l
Nitrogen inerting during and before distillation
Vacuum distillations up to 10 mbar abs. possible
Distillation under reflux with automated liquid distributor possible; setting of different reflux ratios possible

Procedure in the project

Fraunhofer UMSICHT offers an individual approach adapted to the respective project.

Target definition at the beginning of the project
Clarification of the problem and solution
Planning of the experiments (selection of parameters and equipment)
Execution of the experiments
Continuous exchange in order to make adjustments during the project if necessary
Final analysis (internal and external)
Preparation of the report and discussion of the results

Results of the collaboration

At the end of the project there is a detailed project documentation with all experimental parameters and results of the analytics. The samples produced are made available.

Downstream processes for defossilized chemistry