Kinetics of hydrogen peroxide reduction by hydrogen in a microreactor

Voloshin, Yury; Lawal, Adeniyi

doi:10.1016/j.apcata.2008.10.019

Cited by 31 publications

(32 citation statements)

References 27 publications

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“…The industrially used Anthraquinone Process is an indirect route, since anthraquinone acts as an oxygen carrier to On-demand production of hydrogen peroxide in a microreactor at end-user sites was in the goal of investigations reported in [130,131]. Hydrogen peroxide was generated in a microreactor in a gas-liquid-solid process with direct mixing of hydrogen and oxygen (using air), a liquid solvent, and a solid catalyst which included operation in the explosive regime.…”

Section: Oxi-hydrogen Reaction (To Hydrogen Peroxide)mentioning

confidence: 99%

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Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry

2009

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Driven by the economics of scale, the size of reaction vessels as the major processing apparatus of the chemical industry has became bigger and bigger [1,2]. Consequently, the efforts for ensuring mixing and heat transfer have also increased, as these are scale dependent. This has brought vessel operation to (partly severe) technical limits, especially when controlling harsh conditions, e.g., due to large heat releases. Accordingly, processing at a very large scale has resulted in taming of the chemistry involved in order to slow it down to a technically controllable level. Therefore, reaction paths that already turned out too aggressive at the laboratory scale are automatically excluded for later scale-up, which constitutes a common everyday confinement in exploiting chemical transformations. Organic chemists are barely conscious that even the small-scale laboratory protocols in their textbooks contain many slow, disciplined chemical reactions. Operations such as adding a reactant drop by drop in a large diluted solvent volume have become second nature, but are not intrinsic to the good engineering of chemical reactions. These are intrinsic to the chemical apparatus used in the past. In contrast, today's process intensification [3][4][5][6][7][8][9][10][11][12] and the new flow-chemistry reactors on the micro-and milli-scale allow such limitations to be overcome, and thus, enable a complete, ab-initio type rethinking of the processes themselves. In this way, space-time yields and the productivity of the reactor can be increased by orders of magnitude and other dramatic performance step changes can be achieved. A hand-in-hand design of the reactors and process re-thinking is required to enable chemistry rather than subduing chemistry around the reactor [40]. This often leads to making use of process conditions far from conventional practice, under harsh environments, a procedure named here as Novel Process Windows. Starting Point: Novel Process WindowsIntensify Rather than OptimizeThe aim of the following introductory remarks, and the paper as whole, is to make sensible -while everyone in the field would agree that microstructured reactors and micro-process technology [3-12] form a major direction within process intensification -that the exploitation of such innovation can still profit considerably by joining both concepts. It is frequently thought that the use of a microstructured reactor automatically and implicitly results in process intensification; simply because this is a major direction within process intensification and since the latter is also concerned with apparatus developments. This is only partly true and actually ignores significant chances for process breakthrough. In many investigations, the use of a microstructured reactor is still more concerned with process optimization, which is involves a slight to moderate improvement of processes using classical paths, in particular with the same or similar chemical and processing protocol. Often, the most radical and innovative step is the

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Section: Oxi-hydrogen Reaction (To Hydrogen Peroxide)mentioning

confidence: 99%

“…Theoretical studies have determined thermal and kinetic explosion limits of hydrogen/oxygen mixing and showed much wider safe process windows due to better heat transfer and mechanistic radical chain quenching at the channel walls (flame-arrestor effect) [71,[128][129][130], Eq. (1):…”

Section: Oxi-hydrogen Reaction (To Hydrogen Peroxide)mentioning

confidence: 99%

Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry

2009

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“…Micro-packed beds are nowadays commonly used in catalyst testing [7] or kinetic studies of heterogeneously catalyzed reactions [8][9][10] , since they simply allow application of already optimized or conventional catalysts available on the market. Typically, catalyst particles used are in a range of 50-150 µm [7,10] .…”

Section: Introductionmentioning

confidence: 99%

Direct synthesis of hydrogen peroxide using concentrated H2 and O2 mixtures in a wall-coated microchannel – kinetic study

Paunovic

Schouten

Nijhuis

2015

Applied Catalysis A: General

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“…Furthermore, alternative reaction systems such as microreactors [19][20][21][22][23] and catalytic membranes [24][25][26] have been successfully employed in direct synthesis of hydrogen peroxide during the last few years. There are also other systems, such as fuel cells for electrochemical synthesis, [27][28][29][30][31][32][33][34] which strictly speaking can be considered as "direct synthesis" because they only use hydrogen and oxygen, but they are beyond the scope of this review.…”

Section: Tapio O Salmimentioning

confidence: 99%

“…Langmuir-Hinshelwood rate equations for different mechanisms proposed were obtained. Later, they studied the decomposition and hydrogenation reactions 22,83 and were finally able to propose and verify an overall rate expression for H 2 O 2 production in a microreactor.…”

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confidence: 99%

Engineering in direct synthesis of hydrogen peroxide: targets, reactors and guidelines for operational conditions

et al. 2014

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The demand for hydrogen peroxide is booming since it is considered as one of the most environmentally friendly and versatile chemical oxidants available and has a wide range of applications. The annual market, close to 3000 kt per year being produced via the auto-oxidation process (with 2-ethyl anthraquinone (traditional) or amyl anthraquinone for mega-plants), is mostly supplied by the company Solvay (30%), followed by Evonik (20%) and Arkema (13%). Nevertheless, the dream of a direct synthesis process is close to a century old and it has gained momentum in research efforts during the last decade with more than 15 groups active in the world. In this review, we focus the discussion on the targets, e.g. plant tonnage, the reactors and the most feasible industrial operational conditions, based on our experience and point of view using the chemical engineering tools available. Thus, direct synthesis can be competitive when on-site production is required and capacities less than 10 kt per year are He has led and participated in 3 EU, 6 national/regional projects and 10+ SME contracts and has published 30+ research papers. Teresa MorenoTeresa Moreno obtained her degree in Chemical Engineering from Complutense University (Madrid, Spain) and later completed her PhD in Chemical Engineering at the University of Valladolid (Spain, 2011) studying the catalytic direct synthesis of hydrogen peroxide in supercritical CO 2 and the online determination of the product using Raman spectroscopy. She is currently a Research Scientist in the Industrial Bioactive Technologies Group at Callaghan Innovation (New Zealand) working on the development of processes for adding value to natural materials toward high value products and applications, including the development of sustainable technologies using supercritical fluids. View Article OnlineView Journal | View Issue and semi-continuous modes of operation. However, at the moment, demonstrations of continuous operations as well as carefully determined kinetics are needed in order to scale up the process. Finally, operational conditions, including the catalyst composition (active metal, oxidation state and support), promoters (halides and acids-pH-isoelectric point), solvents, pressure and temperature need to be carefully analysed. In our opinion, as we try to show here, H 2 O 2 direct synthesis is a competitive process and is ready for larger scale demonstration. Also, more than a hundred patents within the area support this claim, although the barriers of technology demonstration and further licensing are still pending.

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Kinetics of hydrogen peroxide reduction by hydrogen in a microreactor

Cited by 31 publications

References 27 publications

Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry

Novel Process Windows – Gate to Maximizing Process Intensification via Flow Chemistry

Direct synthesis of hydrogen peroxide using concentrated H2 and O2 mixtures in a wall-coated microchannel – kinetic study

Engineering in direct synthesis of hydrogen peroxide: targets, reactors and guidelines for operational conditions

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