Ultrazvočno intenzivirani reaktorji s fiksno plastjo
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.
Sonicator 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.
- Izboljšan prenos toplote: 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.
Katalizatorji s fiksno plastjo
Fiksne plasti (včasih imenovane tudi pakirana postelja) so običajno obremenjene s katalizatorskimi peleti, ki so običajno granule s premerom od 1 do 5 mm. V reaktor se lahko naložijo v obliki ene postelje, kot ločene lupine ali v ceveh. Katalizatorji večinoma temeljijo na kovinah, kot so nikelj, baker, osmij, platina in rodij.
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.
- Izboljšana učinkovitost
- Povečana reaktivnost
- Povečana stopnja konverzije
- Višji donos
- Recikliranje katalizatorja
Ultrazvočna intenzifikacija katalitičnih reakcij
Ultrazvočno mešanje in mešanje izboljšuje stik med delci reaktanta in katalizatorja, ustvarja visoko reaktivne površine in sproži in / ali izboljša kemično reakcijo.
Ultrazvočna priprava katalizatorja lahko povzroči spremembe v obnašanju kristalizacije, disperziji / deaglomeraciji in površinskih lastnostih. Poleg tega lahko na lastnosti predhodno oblikovanih katalizatorjev vpliva odstranjevanje pasivizirajočih površinskih plasti, boljša disperzija, povečanje prenosa mase.
Examples of Ultrasonically-Improved Reactions
- Ultrazvočna predobdelava Ni katalizatorja za reakcije hidrogeniranja
- Sonicated Raney Ni katalizator z vinsko kislino povzroči zelo visoko enantioselektivnost
- Ultrasonic synthesized Fischer-Tropsch catalysts
- Sonokemično obdelani amorfni praškasti katalizatorji za povečano reaktivnost
- Sonosinteza amorfnih kovinskih prahov
Ultrazvočno izterjava katalizatorja
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 ponuja različne ultrazvočne procesorje in različice za integracijo ultrazvoka moči v reaktorje s fiksno posteljo. Na voljo so različni ultrazvočni sistemi za vgradnjo v reaktorje s fiksno posteljo. Za bolj kompleksne tipe reaktorjev ponujamo Prilagojena ultrazvočna Rešitve.
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!
Kontaktirajte nas še danes! Z veseljem se bomo z vami pogovorili o ultrazvočni intenzifikaciji vašega kemičnega procesa!
V spodnji tabeli je prikazana približna zmogljivost obdelave Hielscherjevih sonikatorjev:
- hidrogeniranje
- Alcylacija
- Cianina
- Eterifikacija
- esterifikacija
- polimerizacija
- Alilacija
- Bromacija
(npr. Ziegler-Nattovi katalizatorji, metaloceni)
Literatura / Reference
- 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.
Dejstva, ki jih je vredno vedeti
Kaj je ultrazvočna kavitacija?
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.
Kaj je sonokemija?
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?
V kemiji se heterogena kataliza nanaša na vrsto katalitične reakcije, kjer se faze katalizatorja in reaktantov med seboj razlikujejo. V kontekstu heterogene kemije se faza ne uporablja le za razlikovanje med trdno, tekočo in plinasto, ampak se nanaša tudi na tekočine, ki se ne mešajo, npr. olje in voda.
Med heterogeno reakcijo se eden ali več reaktantov kemično spremeni na vmesniku, npr. na površini trdnega katalizatorja.
Hitrost reakcije je odvisna od koncentracije reaktantov, velikosti delcev, temperature, katalizatorja in drugih dejavnikov.
Koncentracija reaktanta: Na splošno povečanje koncentracije reaktanta poveča hitrost reakcije zaradi večjega vmesnika in s tem večjega faznega prenosa med delci reaktanta.
Velikost delcev: Če je eden od reaktantov trdni delec, ga ni mogoče prikazati v enačbi hitrosti, saj enačba hitrosti prikazuje samo koncentracije, trdne snovi pa ne morejo imeti koncentracije, ker so v drugi fazi. Vendar pa velikost delcev trdne snovi vpliva na hitrost reakcije zaradi razpoložljive površine za prenos faze.
Reakcijska temperatura: Temperatura je povezana s konstanto hitrosti prek Arrheniusove enačbe: k = Ae-Ea/RT
Kjer je Ea aktivacijska energija, je R univerzalna plinska konstanta in T je absolutna temperatura v Kelvinih. A je Arrheniusov (frekvenčni) faktor. e-Ea/RT daje število delcev pod krivuljo, ki imajo energijo, večjo od aktivacijske energije, Ea.
Katalizator: V večini primerov se reakcije pojavijo hitreje s katalizatorjem, ker zahtevajo manj aktivacijske energije. Heterogeni katalizatorji zagotavljajo površino šablone, na kateri poteka reakcija, medtem ko homogeni katalizatorji tvorijo vmesne produkte, ki sproščajo katalizator v naslednjem koraku mehanizma.
Drugi dejavniki: Drugi dejavniki, kot je svetloba, lahko vplivajo na določene reakcije (fotokemija).
What are the Types of Catalyst Deactivation?
- Zastrupitev s katalizatorjem je izraz za močno kemisorpcijo vrst na katalitičnih mestih, ki blokirajo mesta za katalitično reakcijo. Zastrupitev je lahko reverzibilna ali nepovratna.
- Obraščanje se nanaša na mehansko razgradnjo katalizatorja, kjer se vrste iz tekoče faze odlagajo na katalitično površino in v pore katalizatorja.
- Toplotna razgradnja in sintranje povzročita izgubo katalitske površine, podporne površine in aktivnih fazno-podpornih reakcij.
- Nastajanje hlapov pomeni kemično razgradno obliko, pri kateri plinska faza reagira s katalizatorsko fazo in nastane hlapne spojine.
- Reakcije para-trdna snov in trdna snov povzročijo kemično deaktivacijo katalizatorja. Para, podpora ali promotor reagirajo s katalizatorjem, tako da nastane neaktivna faza.
- Izčrpavanje ali drobljenje delcev katalizatorja povzroči izgubo katalitskega materiala zaradi mehanske obrabe. Notranja površina katalizatorja se izgubi zaradi mehansko povzročenega drobljenja delcev katalizatorja.
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.
Nukleofilno substitucijo lahko opazimo kot dve različni poti – SN1 in SN2 reakcija. Katera oblika reakcijskega mehanizma – sN1 ali SN2 – poteka, je odvisno od strukture kemičnih spojin, vrste nukleofila in topila.

