Catalytic dehydrogenation, of ammonia

Zhou, X., et ah, Deposition ofFe-Ni nanoparticles on polyethyleneimine-decoratedgraphene oxide and application in catalytic dehydrogenation of ammonia borane. Journal of Materials Chemistry, 2012. 22(27) p. 13506-13516. 

Platinum also is used extensively as a catalyst in hydrogenation, dehydrogenation, oxidation, isomerization, carbonylation, and hydrocracking. Also, it is used in organic synthesis and petroleum refining. Like palladium, platinum also exhibits remarkable abdity to absorb hydrogen. An important application of platinum is in the catalytic oxidation of ammonia in Ostwald s process in the manufacture of nitric acid. Platinum is installed in the catalytic converters in automobile engines for pollution control. 

W.G. Frankenburg. The Catalytic Synthesis of Ammonia from Nitrogen and Hydrogen. In P.H. Emmett, editor. Hydrogenation and Dehydrogenation. Catalysis, Volume 3. Reinhold, New York, 1955. 

Catalytic Dehydrogenation of Diethanolamine Monsanto has developed a new method for production of the herbicide that eliminates most manufacturing hazards and all use of cyanide, ammonia, and formaldehyde in the synthesis of the key intermediate, DSIDA. Monsanto s novel catalytic synthesis of DSIDA uses a copper catalyst, and is safer because it is endothermic, produces higher overall yield, and has fewer process steps. 

For more examples of synthetic approaches that have reduced the use of ammonia, see also the case studies describing catalytic dehydrogenation of diethanolamine, HCN-free synthesis of the amino acids, and HCN-free synthesis of the specialty chemical, sarcosinate, all listed under the section on hydrogen cyanide, and the case study describing synthesis of the drug aprepitant. 

Fabrication of Hollow Silica-Alumina Composite Spheres Using L(+)-Arginine and their Catalytic Performance for Hydrolytic Dehydrogenation of Ammonia Borane... 

We have already fabricated hollow silica-alumina composite spheres prepared by sol-gel based method using aqueous ammonia solution as a promoter of sol-gel reaction [4], and have revealed the influence of their nanostructure of the hollow spheres on their catalytic activity for hydrolysis of NH3BH3 [4], In the present study, we fabricated hollow silica-alumina composite spheres using PS template method and investigated their activity for hydrolytic dehydrogenation of ammonia borane. In addition, we firstly fabricated the hollow spheres using L(+)-arginine as the promoter for hydrolysis of tetraethoxysilane (TEOS) [16],... 

Dutch State Mines (Stamicarbon). Vapor-phase, catalytic hydrogenation of phenol to cyclohexanone over palladium on alumina, Hcensed by Stamicarbon, the engineering subsidiary of DSM, gives a 95% yield at high conversion plus an additional 3% by dehydrogenation of coproduct cyclohexanol over a copper catalyst. Cyclohexane oxidation, an alternative route to cyclohexanone, is used in the United States and in Asia by DSM. A cyclohexane vapor-cloud explosion occurred in 1975 at a co-owned DSM plant in Flixborough, UK (12) the plant was rebuilt but later closed. In addition to the conventional Raschig process for hydroxylamine, DSM has developed a hydroxylamine phosphate—oxime (HPO) process for cyclohexanone oxime no by-product ammonium sulfate is produced. Catalytic ammonia oxidation is followed by absorption of NO in a buffered aqueous phosphoric acid... 

A further method for the synthesis of the title compounds with only hydrogen as byproduct is the base-catalyzed dehydrogenative coupling (index D) of ammonia and tris(hydridosilylethyl)boranes, B[C2H4Si(R)H2]3 (R = H, CH3). Initially, the strong base, e.g. n-butyl lithium, deprotonates ammonia. The highly nucleophilic amide replaces a silicon-bonded hydride to form a silylamine and lithium hydride, which then deprotonates ammonia, resuming the catalytic cycle. Under the conditions used, silylamines are not stable and by elimination of ammonia, polysilazane frameworks form. In addition, compounds B[C2l-L Si(R)H2]3 can be obtained from vinylsilanes, H2C=CHSi(R)H2 (R - H, CH3), and borane dimethylsulfide. 

Over 70% of known catalytic reactions involve some form of metallic component. Industrially, metals are used in catalytic reforming, hydrocracking, ammonia and methanol synthesis, indirect coal liquefaction, oxidation, and a vast number of organic hydrogenation and dehydrogenation processes. Academically, metals are favored for research since they are easily prepared in pure form and conveniently characterized. In fact, most of the fundamental information leading to conceptual theories in catalysis originated with studies on metal systems. 

Desulfurization of petroleum feedstock (FBR), catalytic cracking (MBR or FI BR), hydrodewaxing (FBR), steam reforming of methane or naphtha (FBR), water-gas shift (CO conversion) reaction (FBR-A), ammonia synthesis (FBR-A), methanol from synthesis gas (FBR), oxidation of sulfur dioxide (FBR-A), isomerization of xylenes (FBR-A), catalytic reforming of naphtha (FBR-A), reduction of nitrobenzene to aniline (FBR), butadiene from n-butanes (FBR-A), ethylbenzene by alkylation of benzene (FBR), dehydrogenation of ethylbenzene to styrene (FBR), methyl ethyl ketone from sec-butyl alcohol (by dehydrogenation) (FBR), formaldehyde from methanol (FBR), disproportionation of toluene (FBR-A), dehydration of ethanol (FBR-A), dimethylaniline from aniline and methanol (FBR), vinyl chloride from acetone (FBR), vinyl acetate from acetylene and acetic acid (FBR), phosgene from carbon monoxide (FBR), dichloroethane by oxichlorination of ethylene (FBR), oxidation of ethylene to ethylene oxide (FBR), oxidation of benzene to maleic anhydride (FBR), oxidation of toluene to benzaldehyde (FBR), phthalic anhydride from o-xylene (FBR), furane from butadiene (FBR), acrylonitrile by ammoxidation of propylene (FI BR)... 

The benzoic acid might also be made by the Diels-Alder reaction of 1,3-butadiene with acrylic acid followed by catalytic dehydrogenation. Treatment of phenol with ammonia at high temperatures produces aniline, as mentioned in Chap. 2. Ethylbenzene can be rearranged to xylenes with zeolite catalysts. Thus, it could serve as a source of ph-thalic, isophthalic, and terephthalic acids by the oxidation of o, m, and p-xylenes. (The xylenes and other aromatic hydrocarbons can also be made by the dehydrocyclization of ethylene, propylene, and butenes, or their corresponding alkanes.44 Benzene can also be made from methane.195)... 

Figure 2 Volcano plots illustrating how catalytic activities depend on the nature of the metal used as catalyst, (a) Correlation between catalytic activity for formic acid dehydrogenation and enthalpy of formation of metal formates. (Ref. 10. Reproduced by permission of John Wiley Sons, lnc.) (b) Correlation between catalytic activity for ammonia synthesis and degree of d-band filling in the metal used as catalyst. (Ref. 12. Reproduced by permission of John Wiley Sons, Inc.) ...

The modern beginning of the heterogeneous catalytic oxidation of olefins to aldehydes may be taken as the discovery of the oxidation of propylene to acrolein over cuprous oxide by Hearne and Adams (5 ). This reaction has been carried to commercial operation by Shell Chemical Company. More recently, the use of bismuth phosphomolybdate has been demonstrated for the oxidation of propylene to acrolein by Veatch and co-workers (88), and, in the presence of ammonia, to acrylonitrile by Idol (89). It was also shown, by Heame and Furman (90), that diolefins could be made from C4 and higher olefins by oxidative dehydrogenation over a bismuth molybdate catalyst. From these beginnings, information on olefin oxidation has increased very rapidly, both in journal and patent literature. We shall make no attempt to review the large number of patents that have issued, but shall limit ourselves mainly to journal literature. 

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