Ultrasonically Intensified Fixed Bed Reactors
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.
- Perpindahan Panas yang Ditingkatkan: 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.
Katalis Tempat Tidur Tetap
Tempat tidur tetap (kadang-kadang juga disebut tempat tidur yang dikemas) biasanya diisi dengan pelet katalis, yang biasanya berupa butiran dengan diameter 1-5mm. Mereka dapat dimuat ke dalam reaktor dalam bentuk sebagai tempat tidur tunggal, sebagai cangkang terpisah, atau dalam tabung. Katalis sebagian besar didasarkan pada logam seperti nikel, tembaga, osmium, platinum, dan 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.
- Peningkatan efisiensi
- Peningkatan reaktivitas
- Peningkatan tingkat konversi
- hasil yang lebih tinggi
- Daur ulang katalis
Intensifikasi Ultrasonik Reaksi Katalitik
Pencampuran dan agitasi ultrasonik meningkatkan kontak antara partikel reaktan dan katalis, menciptakan permukaan yang sangat reaktif dan memulai dan/atau meningkatkan reaksi kimia.
Persiapan katalis ultrasonik dapat menyebabkan perubahan perilaku kristalisasi, dispersi / deaglomerasi dan sifat permukaan. Selanjutnya, karakteristik katalis yang telah dibentuk sebelumnya dapat dipengaruhi dengan menghilangkan lapisan permukaan pasif, dispersi yang lebih baik, meningkatkan perpindahan massa.
Examples of Ultrasonically-Improved Reactions
- Pra-perlakuan ultrasonik katalis Ni untuk reaksi hidrogenasi
- Katalis Raney Ni yang disonikasi dengan asam tartarat menghasilkan enansioselektivitas yang sangat tinggi
- Ultrasonic synthesized Fischer-Tropsch catalysts
- Katalis bubuk amorf yang diolah secara sonokimia untuk meningkatkan reaktivitas
- Sono-sintesis bubuk logam amorf
Pemulihan Katalis Ultrasonik
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 menawarkan berbagai prosesor ultrasonik dan variasi untuk integrasi ultrasound daya ke dalam reaktor tempat tidur tetap. Berbagai sistem ultrasonik tersedia untuk dipasang ke dalam reaktor tempat tidur tetap. Untuk jenis reaktor yang lebih kompleks, kami menawarkan Ultrasonik yang disesuaikan Solusi.
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!
Hubungi kami hari ini! Kami senang mendiskusikan intensifikasi ultrasonik proses kimia Anda dengan Anda!
Tabel di bawah ini memberi Anda indikasi perkiraan kapasitas pemrosesan sonikator Hielscher:
- Hidrogenasi
- Alsilasi
- Sianasi
- eterifikasi
- esterifikasi
- Polimerisasi
- Alilasi
- Brominasi
(misalnya katalis Ziegler-Natta, metalosen)
Literatur / Referensi
- 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-fakta yang Patut Diketahui
Apa itu Kavitasi ultrasonik?
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.
Apa itu Sonokimia?
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?
Dalam kimia, katalisis heterogen mengacu pada jenis reaksi katalitik di mana fase katalis dan reaktan berbeda satu sama lain. Dalam konteks kimia heterogen, fase tidak hanya digunakan untuk membedakan antara padat, cair, dan gas, tetapi juga mengacu pada cairan yang tidak dapat bercampur, misalnya minyak dan air.
Selama reaksi heterogen, satu atau lebih reaktan mengalami perubahan kimia pada antarmuka, misalnya pada permukaan katalis padat.
Laju reaksi tergantung pada konsentrasi reaktan, ukuran partikel, suhu, katalis, dan faktor lebih lanjut.
Konsentrasi reaktan: Secara umum, peningkatan konsentrasi reaktan meningkatkan laju reaksi karena antarmuka yang lebih besar dan dengan demikian transfer fase yang lebih besar antara partikel reaktan.
Ukuran partikel: Ketika salah satu reaktan adalah partikel padat, maka tidak dapat ditampilkan dalam persamaan laju, karena persamaan laju hanya menunjukkan konsentrasi dan padatan tidak dapat memiliki konsentrasi karena berada dalam fase yang berbeda. Namun, ukuran partikel padatan mempengaruhi laju reaksi karena luas permukaan yang tersedia untuk transfer fase.
Suhu reaksi: Suhu terkait dengan konstanta laju melalui persamaan Arrhenius: k = Ae-Ea/RT
Di mana Ea adalah energi aktivasi, R adalah konstanta gas universal dan T adalah suhu absolut dalam Kelvin. A adalah faktor Arrhenius (frekuensi). e-Ea/RT memberikan jumlah partikel di bawah kurva yang memiliki energi lebih besar dari energi aktivasi, Ea.
Katalisator: Dalam kebanyakan kasus, reaksi terjadi lebih cepat dengan katalis karena membutuhkan lebih sedikit energi aktivasi. Katalis heterogen menyediakan permukaan cetakan di mana reaksi terjadi, sedangkan katalis homogen membentuk produk perantara yang melepaskan katalis selama langkah mekanisme selanjutnya.
Faktor lain: Faktor lain seperti cahaya dapat mempengaruhi reaksi tertentu (fotokimia).
What are the Types of Catalyst Deactivation?
- Keracunan katalis adalah istilah untuk chemisorption yang kuat dari spesies di situs katalitik yang memblokir situs untuk reaksi katalitik. Keracunan bisa reversibel atau ireversibel.
- Pengotoran mengacu pada degradasi mekanis katalis, di mana spesies dari fase fluida mengendap ke permukaan katalitik dan di pori-pori katalis.
- Degradasi termal dan sintering mengakibatkan hilangnya luas permukaan katalitik, area pendukung, dan reaksi pendukung fase aktif.
- Pembentukan uap berarti bentuk degradasi kimia, di mana fase gas bereaksi dengan fase katalis untuk menghasilkan senyawa yang mudah menguap.
- Reaksi uap-padat dan padat-padat menghasilkan penonaktifan kimia katalis. Uap, pendukung, atau promotor bereaksi dengan katalis sehingga menghasilkan fase tidak aktif.
- Gesekan atau penghancuran partikel katalis mengakibatkan hilangnya bahan katalitik karena abrasi mekanis. Luas permukaan internal katalis hilang karena penghancuran partikel katalis yang diinduksi secara mekanis.
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.
Substitusi nukleofilik dapat diamati sebagai dua jalur yang berbeda – Sn1 dan Sn2 reaksi. Bentuk mekanisme reaksi yang mana – Sn1 atau Sn2 – terjadi, tergantung pada struktur senyawa kimia, jenis nukleofil dan pelarut.

