Ultrasoniski intensificēti fiksēto gultu reaktori
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.
- Uzlabota siltuma pārnese: 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.
Fiksētie slāņa katalizatori
Fiksētās gultas (dažreiz sauktas arī par iepakotu gultu) parasti tiek piekrautas ar katalizatora granulām, kas parasti ir granulas ar diametru no 1-5 mm. Tos var ielādēt reaktorā kā vienvietīgu gultu, kā atsevišķus apvalkus vai caurulēs. Katalizatoru pamatā galvenokārt ir tādi metāli kā niķelis, varš, osmijs, platīns un rodijs.
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.
- Uzlabota efektivitāte
- Palielināta reaktivitāte
- Palielināts konversijas līmenis
- Augstāka raža
- Katalizatora pārstrāde
Katalītisko reakciju ultraskaņas pastiprināšana
Ultraskaņas sajaukšana un uzbudinājums uzlabo kontaktu starp reaģenta un katalizatora daļiņām, rada ļoti reaktīvas virsmas un ierosina un / vai uzlabo ķīmisko reakciju.
Ultraskaņas katalizatora sagatavošana var izraisīt kristalizācijas uzvedības, dispersijas / deagglomerācijas un virsmas īpašību izmaiņas. Turklāt iepriekš izveidoto katalizatoru īpašības var ietekmēt, noņemot pasivējošus virsmas slāņus, labāku izkliedi, palielinot masas pārnesi.
Examples of Ultrasonically-Improved Reactions
- Ni katalizatora ultraskaņas pirmapstrāde hidrogenēšanas reakcijām
- Ultraskaņas Raney Ni katalizators ar vīnskābi rada ļoti augstu enantioselectivitāti
- Ultrasonic synthesized Fischer-Tropsch catalysts
- Sonoķīmiski apstrādāti amorfie pulvera katalizatori paaugstinātai reaktivitātei
- Amorfu metālu pulveru sono-sintēze
Ultraskaņas katalizatora atgūšana
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 piedāvā dažādus ultraskaņas procesorus un variācijas jaudas ultraskaņas integrēšanai fiksētās gultas reaktoros. Ir pieejamas dažādas ultraskaņas sistēmas, lai tās uzstādītu fiksētās gultas reaktoros. Sarežģītākiem reaktoru tipiem mēs piedāvājam pielāgota ultraskaņa Risinājumus.
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!
Sazinieties ar mums jau šodien! Mēs esam priecīgi apspriest ar jums jūsu ķīmiskā procesa ultraskaņas intensifikāciju!
Tabulā zemāk ir norādīta aptuvenā Hielscher sonikatoru apstrādes jauda:
- hidrogenēšana
- Alksnēšana
- Cianēšana
- Ēterifikācija
- esterificēšana
- polimerizācija
- Allilācija
- Bromēšana
(piemēram, Ziegler-Natta katalizatori, metallocēni)
Literatūra / Atsauces
- 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.
Fakti, kurus ir vērts zināt
Kas ir ultraskaņas kavitācija?
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.
Kas ir Sonochemistry?
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?
Ķīmijā heterogēna katalīze attiecas uz katalītiskās reakcijas veidu, kurā katalizatora fāzes un reaģenti atšķiras viens no otra. Heterogēnās ķīmijas kontekstā fāzi izmanto ne tikai, lai atšķirtu cietu, šķidru un gāzi, bet tā attiecas arī uz nesajaucamiem šķidrumiem, piemēram, eļļu un ūdeni.
Neviendabīgas reakcijas laikā viens vai vairāki reaģenti saskarnē tiek ķīmiski mainīti, piemēram, uz cieta katalizatora virsmas.
Reakcijas ātrums ir atkarīgs no reaģentu koncentrācijas, daļiņu lieluma, temperatūras, katalizatora un citiem faktoriem.
Reaģentu koncentrācija: Kopumā reaģenta koncentrācijas palielināšanās palielina reakcijas ātrumu, pateicoties lielākai saskarnei un tādējādi lielākai fāzes pārnešanai starp reaktīvajām daļiņām.
Daļiņu izmērs: Ja viens no reaģentiem ir cieta daļiņa, tad to nevar parādīt ātruma vienādojumā, jo ātruma vienādojums parāda tikai koncentrācijas un cietām vielām nevar būt koncentrācija, jo tās atrodas citā fāzē. Tomēr cietās vielas daļiņu izmērs ietekmē reakcijas ātrumu, jo fāzes pārnešanai ir pieejams virsmas laukums.
Reakcijas temperatūra: Temperatūra ir saistīta ar ātruma konstanti, izmantojot Arrhenius vienādojumu: k = Ae-Ea/RT
Kur Ea ir aktivācijas enerģija, R ir universālā gāzes konstante un T ir absolūtā temperatūra kelvinos. A ir Arrhenius (frekvences) koeficients. e-Ea/RT dod daļiņu skaitu zem līknes, kuru enerģija ir lielāka nekā aktivācijas enerģija, Ea.
Katalizators: Vairumā gadījumu reakcijas notiek ātrāk ar katalizatoru, jo tām nepieciešama mazāka aktivācijas enerģija. Heterogēnie katalizatori nodrošina veidnes virsmu, pie kuras notiek reakcija, savukārt viendabīgi katalizatori veido starpproduktus, kas atbrīvo katalizatoru nākamajā mehānisma posmā.
Citi faktori: Citi faktori, piemēram, gaisma, var ietekmēt noteiktas reakcijas (fotoķīmija).
What are the Types of Catalyst Deactivation?
- Katalizatora saindēšanās ir termins, ar ko apzīmē sugu spēcīgu ķīmisko izsorbciju katalītiskajās vietās, kas bloķē katalītiskās reakcijas vietas. Saindēšanās var būt atgriezeniska vai neatgriezeniska.
- Piesārņojums attiecas uz katalizatora mehānisku noārdīšanos, kad sugas no šķidrās fāzes nogulsnējas uz katalītiskās virsmas un katalizatora porās.
- Termiskās noārdīšanās un saķepināšanas rezultātā tiek zaudēts katalītiskais virsmas laukums, atbalsta laukums un aktīvās fāzes atbalsta reakcijas.
- Tvaika veidošanās nozīmē ķīmisku noārdīšanās formu, kurā gāzes fāze reaģē ar katalizatora fāzi, lai radītu gaistošus savienojumus.
- Tvaika–cietas un cietas–cietas reakcijas izraisa katalizatora ķīmisko dezaktivāciju. Tvaiks, atbalsts vai veicinātājs reaģē ar katalizatoru tā, ka rodas neaktīva fāze.
- Katalizatora daļiņu saspiešana vai saspiešana izraisa katalītiskā materiāla zudumu mehāniskās nobrāzuma dēļ. Katalizatora iekšējās virsmas laukums tiek zaudēts katalizatora daļiņas mehāniski inducētas saspiešanas dēļ.
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.
Nukleofilo substitūciju var novērot kā divus dažādus ceļus – SN1 un SN2 reakcija. Kāda veida reakcijas mehānisms – sN1 vai SN2 – notiek, ir atkarīgs no ķīmisko savienojumu struktūras, nukleofila veida un šķīdinātāja.

