Oxidation reactions in the synthesis of fine and intermediate chemicals using environmentally benign oxidants and the right reactor system

2000 ◽  
Vol 72 (7) ◽  
pp. 1273-1287 ◽  
Author(s):  
Wolfgang F. Hoelderich ◽  
Felix Kollmer
Keyword(s):  
Gas Phase ◽  
Heterogeneous Catalysts ◽  
Environmentally Benign ◽  
Oxidation Reactions ◽  
Direct Oxidation ◽  
Oxidation Processes ◽  
Bulk Chemicals ◽  
The Right ◽  
Catalyzed Oxidation ◽  
Oxygenated Products

This review outlines several approaches for designing new and environmentally friendly heterogeneously catalyzed oxidation processes for the synthesis of fine and intermediate chemicals. Environmentally benign oxidants such as molecular oxygen, hydrogen peroxide or nitrous oxide can be activated on suitable heterogeneous catalysts showing high activity and selectivity toward the desired oxygenated products. Several examples illustrate that features known from the synthesis of bulk chemicals can successfully be applied for manufacturing intermediate and specialty chemicals applying conventional industrial reactor systems. Direct oxidation of isoprenol, b-picoline, and benzene are chosen as examples for continuous gas-phase processes, oxidation of pinene and propylene as examples for semi-continuous or batchwise processes in the liquid phase.

scholarly journals Unprecedented and Scalable Copper (I)-Catalyzed Oxidation of the Csp2-H bond on 2-phenyl-naphthalene-1,3-diol with Atmospheric Oxygen: synthesis of 2-Hydroxy-3-phenyl-1,4-naphthoquinone via direct Csp2-O bond formation

2017 ◽  
Vol 27 (5) ◽  
pp. 62-68 ◽  
Author(s):  
Sheila Teresita Guardado-Cruz ◽  
Rafael Ortiz-Alvarado ◽  
Claudia De León ◽  
César Rogelio Solorio-Alvarado
Keyword(s):  
Total Synthesis ◽  
Atmospheric Oxygen ◽  
Bond Formation ◽  
Hypervalent Iodine ◽  
Direct Oxidation ◽  
Oxidative Dimerization ◽  
Reaction Conditions ◽  
Oxidation Processes ◽  
Dimerization Product ◽  
Catalyzed Oxidation

The Csp2-O bond formation via direct oxidation of the Csp2-H bond on electron-rich compounds such as naphthols, is a process that generally requires drastic reaction conditions like high temperature or pressure. Addition of strong oxidants as H2O2, hypervalent iodine reagents (λ3 o λ5), expensive transition metals or rare earth elements, such as Mo, Ru Pt or Ce, is usually necessary. As part of this study on oxidative dimerization of phenols towards the total synthesis of ningalin D, 1,3-naphthalenediol was explored as starting material using stoichiometric amounts of Cu(I) and atmospheric molecular oxygen. A novel two-step sequence reaction for the formation of a 1,4-naphthoquinone was found instead of a dimerization product. The synthesis of this compound involves two consecutive oxidation processes. 

The Activity of Iron-Containing Zeolitic Materials for the Catalytic Oxidation in Aqueous Solutions

2007 ◽  
Vol 555 ◽  
pp. 213-218 ◽  
Author(s):  
Maja Milojević ◽  
V. Dondur ◽  
Lj. Damjanović ◽  
Vesna Rakić ◽  
Nena Rajić ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Heterogeneous Catalysts ◽  
Wet Oxidation ◽  
Oxidation Reactions ◽  
Hydrothermal Crystallization ◽  
Tetrahedral Framework ◽  
Oxidation Processes ◽  
Attractive Option ◽  
Catalytically Active ◽  
Zeolitic Materials

In this work, a series of iron-containing zeolitic materials has been tested as heterogeneous catalysts for decomposition of H2O2 and for oxidation of the cationic dye Methylene Blue with H2O2 in aqueous solutions. FeAPO and FeBEA zeolites, synthesized through hydrothermal crystallization of basic hydrogels, and FeY and FeZSM-5 zeolites, prepared by ionexchange procedures, have been studied. The ion exchange with Fe(III) cations was performed from different salt solutions. Fe-exchange procedure carried out in Fe-citrate solution has been identified as an attractive option for the preparation of highly effective FeZSM-5 catalysts in wet oxidation processes. It has been shown that both tetrahedral, framework Fe, and octahedral, extra-framework Fe species incorporated into zeolite structure are catalytically active in wet oxidation reactions.

Residual Gas Reactions in the Electron Microscope: I. Qualitative Observations on the Water Gas Reaction

1968 ◽  
Vol 26 ◽  
pp. 292-293
Author(s):  
Richard E. Hartman ◽  
Roberta S. Hartman ◽  
Peter L. Ramos
Keyword(s):  
Electron Beam ◽  
Electron Microscope ◽  
Gas Phase ◽  
Absolute Temperature ◽  
Residual Gas ◽  
Gas Reactions ◽  
Image Position ◽  
The Right ◽  
Water Gas ◽  
Thinning Rate

The action of water and the electron beam on organic specimens in the electron microscope results in the removal of oxidizable material (primarily hydrogen and carbon) by reactions similar to the water gas reaction .which has the form:The energy required to force the reaction to the right is supplied by the interaction of the electron beam with the specimen.The mass of water striking the specimen is given by:where u = gH2O/cm2 sec, PH2O = partial pressure of water in Torr, & T = absolute temperature of the gas phase. If it is assumed that mass is removed from the specimen by a reaction approximated by (1) and that the specimen is uniformly thinned by the reaction, then the thinning rate in A/ min iswhere x = thickness of the specimen in A, t = time in minutes, & E = efficiency (the fraction of the water striking the specimen which reacts with it).

Platinum Group Metal Phosphides as Heterogeneous Catalysts for the Gas-Phase Hydroformylation of Small Olefins

ACS Catalysis ◽  
2017 ◽  
Vol 7 (5) ◽  
pp. 3584-3590 ◽  
Author(s):  
Luis Alvarado Rupflin ◽  
Jaroslaw Mormul ◽  
Michael Lejkowski ◽  
Sven Titlbach ◽  
Rainer Papp ◽  
...  
Keyword(s):  
Gas Phase ◽  
Heterogeneous Catalysts ◽  
Platinum Group Metal ◽  
Group Metal ◽  
Metal Phosphides ◽  
Platinum Group

Gas phase interaction with catalytic oxidation reactions

1972 ◽  
Vol 326 (1565) ◽  
pp. 215-227 ◽  
Keyword(s):  
Carbon Dioxide ◽  
Maleic Anhydride ◽  
Catalytic Oxidation ◽  
Gas Phase ◽  
Major Part ◽  
Oxidation Reactions ◽  
Mixed Gas ◽  
Kinetics Of ◽  
Oxidation Of Benzene ◽  
Homogeneous Decomposition

Studies of the catalytic oxidation of benzene to maleic anhydride and carbon dioxide over vanadia/molybdena catalysts show that the major part of the reaction involves interacting gas and gas-solid processes. The results are consistent with a mechanism in which a benzeneoxygen adduct is formed catalytically, desorbs and then reacts to give maleic anhydride entirely in the gas phase. On the basis of this proposed mechanism, the kinetics of individual reactions have been investigated in some depth. The over-oxidation of maleic anhydride has been found to be not significant under the conditions of reaction. The kinetic relationships governing the homogeneous decomposition of the adduct and the oxidation of the adduct to maleic anhydride and to carbon dioxide have been established. The results show that essentially all of the anhydride originates from mixed gas-solid/gas reaction while substantial amounts of carbon dioxide are produced entirely catalytically.

Gas phase hydroformylation of ethylene using organometalic Rh-complexes as heterogeneous catalysts

2005 ◽  
Vol 101 (1-2) ◽  
pp. 43-47 ◽  
Author(s):  
V.I. Zapirtan ◽  
B.L. Mojet ◽  
J.G. van Ommen ◽  
J. Spitzer ◽  
L. Lefferts
Keyword(s):  
Gas Phase ◽  
Heterogeneous Catalysts

Laser electrodispersion as a new chlorine-free method for the production of highly effective metal-containing supported catalysts

2012 ◽  
Vol 84 (3) ◽  
pp. 495-508 ◽  
Author(s):  
Ekaterina S. Lokteva ◽  
Anton A. Peristyy ◽  
Natalia E. Kavalerskaya ◽  
Elena V. Golubina ◽  
Lada V. Yashina ◽  
...  
Keyword(s):  
Gas Phase ◽  
High Stability ◽  
Heterogeneous Catalysts ◽  
Supported Catalysts ◽  
Promising Technique ◽  
Wet Impregnation ◽  
Oxide Supports ◽  
Highly Active ◽  
Specific Catalytic Activity ◽  
Free Metal

Laser electrodispersion (LED) of metals is a promising technique for the preparation of heterogeneous catalysts as an alternative to wet impregnation of supports with the corresponding salt solutions. The LED technique can be used to deposit highly active chloride- and nitrate-free metal nanoparticles onto carbon or oxide supports. We report preparation and properties of new Ni-, Pd-, and Au-containing alumina-supported catalysts with low metal loadings (10–3–10–4 % mass) and their comparison with the previously studied carbon (Sibunit) supported systems. The catalysts demonstrate high stability and extremely high specific catalytic activity (by 2–3 orders of magnitude higher than for traditional catalysts) in the gas-phase hydrodechlorination (HDC) of chlorobenzene (CB).

A facile approach to fabricate halloysite/metal nanocomposites with preformed and in situ synthesized metal nanoparticles: a comparative study of their enhanced catalytic activity

2015 ◽  
Vol 44 (19) ◽  
pp. 8906-8916 ◽  
Author(s):  
Sankar Das ◽  
Subhra Jana
Keyword(s):  
Catalytic Activity ◽  
Comparative Study ◽  
Metal Nanoparticles ◽  
Heterogeneous Catalysts ◽  
Cost Effective ◽  
Environmentally Benign ◽  
Metal Nanocomposites

Halloysite/metal nanocomposites have been synthesized through the immobilization of preformed and in situ synthesized metal nanoparticles over halloysite surfaces, which in turn produce efficient, cost-effective, and environmentally benign heterogeneous catalysts.

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