Ultralydsforstærkede reaktorer med fast leje
Sonication can improve catalytic reactions in fixed-bed reactors mainly by intensifying mass transfer around and inside the packed catalyst bed. Additionally, sonication removes passivation and fouling layers from the catalyst surface thereby continuously regenerating the catalyst.
How Sonication Improves Fixed-Bed Catalysis
In a fixed-bed reactor, the catalyst particles remain stationary while liquid, gas, or multiphase reactants flow through the bed. Reaction performance is often limited by external mass transfer, pore diffusion, channeling, fouling, and heat-transfer gradients. Ultrasound can reduce several of these limitations by generating acoustic cavitation, microstreaming, shear forces, and pressure oscillations.
Soniker UIP2000hdT integrated in a fixed bed reactor
Key Effects of Ultrasonically-Intensified Fixed Bed Reactions
- Improved external mass transfer: Ultrasonic microstreaming reduces the stagnant boundary layer around catalyst particles, allowing reactants to reach active sites more efficiently.
- Enhanced pore accessibility: Cavitation-induced pressure fluctuations and liquid movement can improve penetration of reactants into catalyst pores and removal of products from pores.
- Reduction of fouling and passivation: Sonication can help remove deposits, polymer films, coke precursors, or other passivating layers from catalyst surfaces, maintaining catalytic activity for longer.
- Reduced channeling in packed beds: In micropacked-bed studies, ultrasound has been shown to modify flow behavior and reduce dispersion, helping the reactor approach more ideal plug-flow behavior.
- Forbedret varmeoverførsel: Acoustic streaming and turbulence improve local heat dissipation, reducing hot spots or cold zones in the catalyst bed.
- Higher conversion and yield: By improving mass transfer and catalyst accessibility, sonication can increase reaction rate, conversion, and product yield, especially when the reaction is transport-limited rather than purely kinetically limited.
Improved liquid-solid contact: Ultrasound promotes better wetting of catalyst particles, which is especially useful in trickle-bed, slurry-fed, or liquid-phase fixed-bed systems.
How does Sonication Improve Fixed Bed Catalysis?
The main mechanism is acoustic cavitation: ultrasonic waves create microscopic bubbles that grow and collapse violently. Their collapse generates local shear, microjets, shockwaves, and intense mixing. Near catalyst surfaces, these effects can clean, activate, and refresh the solid-liquid interface. Reviews of sonocatalysis describe this as a synergy between ultrasound and solid catalysts, involving improved heat transfer, mass transfer, and localized effects at catalytic surfaces.
Sonication is most beneficial when the fixed-bed reaction suffers from:
- slow diffusion into catalyst pores,
- poor wetting of catalyst particles,
- product accumulation inside pores,
- fouling or surface passivation,
- mass-transfer-limited kinetics,
- multiphase flow maldistribution,
- channeling through the packed bed.
Katalysatorer med fast leje
Faste senge (nogle gange også kaldet pakket bed) er almindeligvis fyldt med katalysatorpiller, som normalt er granulater med diametre fra 1-5 mm. De kan læsses ind i reaktoren i form af et enkelt leje, som separate skaller eller i rør. Katalysatorerne er for det meste baseret på metaller som nikkel, kobber, osmium, platin og rhodium.
The effects of power ultrasound on heterogeneous chemical reactions are well known and widely used for industrial catalytic processes. Catalytic reactions in a fixed bed reactor benefit from sonication treatment, too. Ultrasonic irradiation of the fixed bed catalyst generates highly reactive surfaces, increases the mass transport between liquid phase (reactants) and catalyst, and removes passivating coatings (e.g. oxide layers) from the surface.
- Forbedret effektivitet
- Øget reaktivitet
- Øget konverteringsrate
- Højere udbytte
- Genanvendelse af katalysator
Ultralydsintensivering af katalytiske reaktioner
Ultralydsblanding og omrøring forbedrer kontakten mellem reaktant- og katalysatorpartikler, skaber meget reaktive overflader og initierer og / eller forbedrer den kemiske reaktion.
Ultralydskatalysatorforberedelse kan forårsage ændringer i krystallisationsadfærd, dispersion / deagglomerering og overfladeegenskaber. Desuden kan egenskaberne ved præformede katalysatorer påvirkes ved at fjerne passiverende overfladelag, bedre dispersion, øge masseoverførslen.
Examples of Ultrasonically-Improved Reactions
- Ultralydsforbehandling af Ni-katalysator til hydrogeneringsreaktioner
- Sonikeret Raney Ni-katalysator med vinsyre resulterer i en meget høj enantioselektivitet
- Ultrasonic synthesized Fischer-Tropsch catalysts
- Sonokemisk behandlede amorfe pulverkatalysatorer for øget reaktivitet
- Sono-syntese af amorfe metalpulvere
Gendannelse af ultralydskatalysator
Solid catalysts in fixed-bed reactors are commonly used in the form of spherical beads, pellets, extrudates, or cylindrical particles. During chemical reactions, the catalyst surface can become passivated by a fouling layer, resulting in a gradual loss of catalytic activity and/or selectivity over time.
The timescale of catalyst deactivation varies considerably. For example, the deactivation of a cracking catalyst may occur within seconds, whereas an iron catalyst used in ammonia synthesis may remain active for 5–10 years. Nevertheless, catalyst deactivation is observed in virtually all catalytic processes. Although different deactivation mechanisms can occur – including chemical, mechanical, and thermal degradation – fouling is one of the most common causes of catalyst decay.
Fouling refers to the physical deposition of species from the fluid phase onto the catalyst surface and within its pores. These deposits block reactive sites, restrict pore accessibility, and reduce contact between reactants and the active catalyst surface. Catalyst fouling by coke or carbonaceous deposits is often a rapid process; however, in many cases it can be partially or fully reversed by ultrasonic regeneration.
Ultrasonic cavitation is an effective method for removing passivating fouling layers from catalyst surfaces. During sonication, high-intensity ultrasound generates cavitation bubbles in a liquid medium. Their collapse produces localized shear forces, microjets, shock waves, and intense micro-mixing. These effects help detach fouling residues from the catalyst surface, reopen blocked pores, and restore access to active sites.
Ultrasonic catalyst recovery is typically carried out by dispersing the catalyst particles in a liquid, such as deionized water or a suitable solvent, and exposing the suspension to controlled ultrasonic treatment. This process can remove fouling residues from various catalyst materials, including platinum/silica fibre catalysts, nickel catalysts, and other supported metal catalysts. As a result, sonication can contribute to catalyst regeneration, extended catalyst lifetime, and improved process sustainability.
Click here to learn more about the ultrasonic regeneration of spent catalysts!
Sonicators for the Integration into Chemical Reactors
Hielscher Ultrasonics tilbyder forskellige ultralydsprocessorer og variationer til integration af ultralyd i reaktorer med fast leje. Forskellige ultralydssystemer er tilgængelige til installation i reaktorer med fast bed. Til mere komplekse reaktortyper tilbyder vi Tilpasset ultralyd Løsninger.
Learn how sonication improves chemical reactions in various reactor designs!
To test the effects of sonication on your chemical reaction, you are welcome to visit our ultrasonic process lab and technical center in Teltow!
Kontakt os i dag! Vi er glade for at diskutere ultralydsintensiveringen af din kemiske proces med dig!
Tabellen nedenfor giver dig en indikation af den omtrentlige behandlingskapacitet for Hielschers sonikatorer:
- Hydrogenering
- Alcylering
- Cyanering
- Etherificering
- Esterificering
- polymerisering
- Allylering
- Bromering
(f.eks. Ziegler-Natta-katalysatorer, metallocener)
Litteratur / Referencer
- Francisco J. Navarro-Brull; Andrew R. Teixeira; Jisong Zhang; Roberto Gómez; Klavs F. Jensen (2018): Reduction of Dispersion in Ultrasonically-Enhanced Micropacked Beds. Industrial & Engineering Chemistry Research 57, 1; 2018. 122–128.
- Yasuo Tanaka (2002): A dual purpose packed-bed reactor for biogas scrubbing and methane-dependent water quality improvement applying to a wastewater treatment system consisting of UASB reactor and trickling filter. Bioresource Technology, Volume 84, Issue 1, 2002. 21-28.
- Argyle, M.D.; Bartholomew, C.H. (2015): Heterogeneous Catalyst Deactivation and Regeneration: A Review. Catalysts 2015, 5, 145-269.
- Oza, R.; Patel, S. (2012): Recovery of Nickel from Spent Ni/Al2O3 Catalysts using Acid Leaching, Chelation and Ultrasonication. Research Journal of Recent Sciences Vol. 1; 2012. 434-443.
- Sana, S.; Rajanna, K.Ch.; Reddy, K.R.; Bhooshan, M.; Venkateswarlu, M.; Kumar, M.S.; Uppalaiah, K. (2012): Ultrasonically Assisted Regioselective Nitration of Aromatic Compounds in Presence of Certain Group V and VI Metal Salts. Green and Sustainable Chemistry, 2012, 2, 97-111.
- Suslick, K. S.; Skrabalak, S. E. (2008): “Sonocatalysis” In: Handbook of Heterogeneous Catalysis, vol. 4; Ertl, G.; Knözinger, H.; Schüth, F.; Weitkamp, J., (Eds.). Wiley-VCH: Weinheim, 2008. 2006-2017.
Fakta, der er værd at vide
Hvad er ultralydskavitation?
Ultrasonic cavitation is the formation, growth and violent collapse of microscopic vapor or gas bubbles in a liquid exposed to high-intensity ultrasound. During bubble collapse, extreme local conditions can occur for very short times, including high temperature, high pressure, shock waves, microjets and intense shear forces.
Hvad er sonokemi?
Sonochemistry is the use of these ultrasonic cavitation effects to initiate, accelerate or modify chemical and physicochemical processes. It is especially relevant in liquid-phase systems because cavitation enhances mixing, mass transfer, emulsification, particle dispersion, catalyst surface cleaning and, in some cases, radical formation. As a result, sonochemistry is used to intensify reactions such as heterogeneous catalysis, oxidation, extraction, polymerization, crystallization and nanomaterial synthesis.
What is a Heterogeneous Catalytic Reaction?
I kemi refererer heterogen katalyse til den type katalytisk reaktion, hvor faserne af katalysatoren og reaktanterne adskiller sig fra hinanden. I forbindelse med heterogen kemi bruges fase ikke kun til at skelne mellem fast, flydende og gas, men det refererer også til ikke-blandbare væsker, f.eks. olie og vand.
Under en heterogen reaktion gennemgår en eller flere reaktanter en kemisk ændring ved en grænseflade, f.eks. på overfladen af en fast katalysator.
Reaktionshastigheden afhænger af koncentrationen af reaktanter, partikelstørrelsen, temperaturen, katalysatoren og yderligere faktorer.
Reaktant koncentration: Generelt øger en stigning i koncentrationen af en reaktant reaktionshastigheden på grund af den større grænseflade og derved større faseoverførsel mellem reaktantpartikler.
Partikelstørrelse: Når en af reaktanterne er en fast partikel, kan den ikke vises i hastighedsligningen, da hastighedsligningen kun viser koncentrationer, og faste stoffer ikke kan have en koncentration, da de er i en anden fase. Imidlertid påvirker partikelstørrelsen af det faste stof reaktionshastigheden på grund af det tilgængelige overfladeareal til faseoverførsel.
Reaktionstemperatur: Temperaturen er relateret til hastighedskonstanten via Arrhenius-ligningen: k = Ae-Ea/RT
Hvor Ea er aktiveringsenergien, er R den universelle gaskonstant og T er den absolutte temperatur i Kelvin. A er Arrhenius-faktoren (frekvens). e-Ea/RT angiver antallet af partikler under kurven, der har energi større end aktiveringsenergien, Ea.
Katalysator: I de fleste tilfælde sker reaktioner hurtigere med en katalysator, fordi de kræver mindre aktiveringsenergi. Heterogene katalysatorer giver en skabelonoverflade, hvor reaktionen finder sted, mens homogene katalysatorer danner mellemprodukter, der frigiver katalysatoren under et efterfølgende trin i mekanismen.
Andre faktorer: Andre faktorer såsom lys kan påvirke visse reaktioner (fotokemi).
What are the Types of Catalyst Deactivation?
- Katalysatorforgiftning er betegnelsen for den stærke kemisorption af arter på katalytiske steder, der blokerer steder for katalytisk reaktion. Forgiftning kan være reversibel eller irreversibel.
- Tilsmudsning refererer til en mekanisk nedbrydning af katalysatoren, hvor arter fra væskefase aflejres på den katalytiske overflade og i katalysatorporer.
- Termisk nedbrydning og sintring resulterer i tab af katalytisk overfladeareal, støtteareal og aktive fasestøttereaktioner.
- Dampdannelse betyder en kemisk nedbrydningsform, hvor gasfasen reagerer med katalysatorfasen for at producere flygtige forbindelser.
- Damp-faste og faste-faste reaktioner resulterer i kemisk deaktivering af katalysatoren. Damp, støtte eller promotor reagerer med katalysatoren, så der produceres en inaktiv fase.
- Nedslidning eller knusning af katalysatorpartiklerne resulterer i tab af katalytisk materiale på grund af mekanisk slid. Katalysatorens indre overfladeareal går tabt på grund af mekanisk induceret knusning af katalysatorpartiklen.
Read more about how sonication can reactivate spent catalysts!
What is Nucleophilic Substitution?
Nucleophilic substitution is a fundamental class of reactions in organic (and inorganic) chemistry, in which a nucleophile selectively bonds in form of a Lewis base (as electron pair donator) with an organic complex with or attacks the positive or partially positive (+) charge of an atom or a group of atoms to replace a leaving group. The positive or partially positive atom, which is the electron pair acceptor, is called an electrophile. The whole molecular entity of the electrophile and the leaving group is usually called the substrate.
Den nukleofile substitution kan observeres som to forskellige veje – SN1 og SN2 reaktion. Hvilken form for reaktionsmekanisme – sN1 eller SN2 – finder sted, afhænger af strukturen af de kemiske forbindelser, typen af nukleofil og opløsningsmidlet.

