Generation of hydrogen peroxide directly from H2 and O2 using CO2 as the solvent

Hâncu, Dan; Beckman, Eric J.

doi:10.1039/b008515o

Cited by 79 publications

(51 citation statements)

References 11 publications

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“…However, CO 2 has the advantage that the effect is reversible since upon depressurisation the CO 2 is degassed from the hydrogen peroxide solution and hence it operates as a reversible in situ promoter. This effect of in situ acid generation using CO 2 in the direct hydrogen peroxide synthesis has also been observed in previous studies by Hâncu and Beckman, 115 and we consider that the use of CO 2 could be highly beneficial in the direct hydrogen peroxide synthesis reaction. We have investigated the structure of the active Au-Pd catalysts in detail, particularly using transmission electron microscopy.…”

Section: -114supporting

confidence: 55%

Heterogeneous catalysts—discovery and design

Hutchings

2009

J. Mater. Chem.

150

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Heterogeneous catalysis plays a key role in the manufacture of essential products in key areas of agriculture and pharmaceuticals, but also in the production of polymers and numerous essential materials. Our understanding of heterogeneous catalysts is advancing rapidly, especially by using the latest characterisation methods on these relatively complex effect materials. At the heart of these catalytic processes, both selective oxidation and hydrogenation play a key role. Both oxidation and hydrogenation exhibit similar requirements since often a partial reaction product is required, rather than the products of total hydrogenation or oxidation, in the latter case this being typically carbon dioxide and water. This Feature Article considers the approaches available for catalyst discovery and design for heterogeneous catalysts. Three catalysts are considered in detail, two exemplifying oxidation and the other selective hydrogenation. The design of vanadium phosphates for the selective oxidation of butane to maleic anhydride is described in terms of the search for advanced materials with superior activity. This is achieved through the synthesis of wholly amorphous vanadium phosphates. The design of supported gold and gold palladium alloy catalysts for the oxidation of carbon monoxide and the direct hydrogenation of oxygen to form hydrogen peroxide is described and the problems concerning selectivity control are discussed.

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Section: -114supporting

confidence: 55%

Heterogeneous catalysts—discovery and design

Hutchings

2009

J. Mater. Chem.

150

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“…Hâncu et al 45 who took a different approach and tried a pre-activation process consisting of particle surface oxidation: the zirconia supported Pd catalyst was reduced in situ by passing a pure hydrogen flow into the reaction medium, and then pure oxygen was fed. After removing excess oxygen, the H 2 /air/N 2 mixture was fed and H 2 O 2 synthesis started.…”

Section: Oxidation Statementioning

confidence: 99%

“…As Centi et al emphasized, nowadays in reality, almost all the research groups have abandoned this idea and operate in the inherently safer gas concentration interval. 5 [45][46][47][48][49][50][51][52][53][54] Generally, the reactor volumes used have been varied from 50 to 600 mL. As a common safety measure in all the systems where the catalyst is a powder, a slurry with a solvent or deionised water has been prepared before feeding the gaseous reactants since upon contact a H 2 -O 2 mixture and a dry Pd-catalyst may result in an explosion.…”

Section: Tapio O Salmimentioning

confidence: 99%

“…Beckman and co-workers 53 first achieved the direct synthesis of H 2 O 2 in liquid CO 2 following a Pd-catalysed hydrogenation and a subsequent oxidation process of fluorinated and, therefore, CO 2 -philic anthraquinone. Later, they developed CO 2 soluble Pd catalysts, 45 obtaining 30-40% yields after 3 hours when using a Pd 2+ catalyst (22°C, 17.0 MPa). They also found the activity of the reduced catalyst to be approximately twice that of the unreduced catalyst.…”

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confidence: 99%

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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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“…The direct synthesis of H 2 O 2 from H 2 and O 2 is a possible way towards small scale plants that may potentially half the cost of hydrogen peroxide with respect to the commercial process [2]. Clearly, the contact between H 2 and O 2 is a significant safety hazard and, at present, no commercial processes have been developed despite several patents [3][4][5][6][7][8][9] and recent literature [10][11][12][13][14][15]. In addition another major problem associated with the process is the generally low H 2 O 2 selectivity.…”

Section: Introductionmentioning

confidence: 99%