Francis Joseph Waller

Methanol technology developments for the new millennium

Abstract This contribution to the “special issue” of Applied Catalysis A: General entitled “Industrial catalytic processes” deals with the development of the methanol process during the last 10–15 years. Following a brief review of the history, the developments to improve methanol synthesis are presented along the lines of elements of catalyst system improvements and of reactor improvements.

Novel technology for the synthesis of dimethyl ether from syngas

Abstract A novel process for producing dimethyl ether (DME) from synthesis gas in a single-step reaction sequence has been developed. The new process uses a slurry reactor in which methanol synthesis, methanol dehydration to DME, and water-gas shift reactions all proceed concurrently. All three reactions are exothermic and reversible. Operation with a back-mixed slurry reactor exploits synergisms of the three reactions, and moderates the reaction exotherm to permit higher conversion of the syngas to liquid products than could be achieved from the three reactions practiced separately. The process offers potential lower capital and operating costs than processes using individual shift, methanol, and DME reaction stages. Process development to-date has focused on the use of coal-derived synthesis gas that is rich in CO. Catalysts used in the process can be a physical mixture of methanol, shift, and dehydration catalysts. Selection of commercially available catalysts and the effect of their different ratios have been investigated. Some process variable results are presented. Commercial applications of the new process are illustrated. Further development of the process is currently underway. In the laboratory, the effects of temperature and feed composition are being studied in detail. Catalyst aging characteristics are also being defined. In addition, plans are being made to demonstrate the process in the Department of Energys Alternative Fuels Development Unit at LaPorte, Texas.

Hafnium(IV) and zirconium(IV) triflates as superior recyclable catalysts for the atom economic nitration of o-nitrotoluene

Abstract The hydrated group 4 metal triflates, Hf(OTf)4 and Zr(OTf)4, were found to be excellent catalysts (10 mol%) for the mononitration of o-nitrotoluene using a single equivalent of concentrated (69%) nitric acid. The only side product is water and the catalysts are readily recycled from the aqueous phase and re-used.

Lanthanide(iii) triflates as recyclable catalysts for atom economic aromatic nitration

Lanthanide(III) triflates catalyse (1–10 mol%) the nitration of a range of simple aromatic compounds in good to excellent yield using stoichiometric quantities of 69% nitric acid; the only by-product is water and the catalyst can be readily recycled by simple evaporation.

Aldehyde/olefin cooxidations: Parallel epoxidation pathways and concerted decomposition of the peroxyacyl-olefin adduct

Abstract Aldehyde-mediated olefin epoxidations appear to proceed by parallel peracid and radical addition pathways. For that portion of the reaction proceeding by radical addition, several lines of evidence favor an explanation in which the peroxyacyl-olefin adduct decomposes in a concerted manner to form alkyl radical, CO 2 , and epoxide.

Epoxidation of alkenes by ozone catalysed by Fe(TMP)Cl

Abstract The epoxidation of a number of cyclic and linear terminal alkenes by an O 2 –O 3 mixture at room temperatures catalysed by Fe(TMP)Cl is reported. It appears that the alkene forms a primary ozonide which rearranges to a secondary ozonide, and it is the latter which, when catalysed by Fe(TMP)Cl, affects the subsequent alkene epoxidation. A number of other metal complexes were also tested as catalysts, but Fe(TMP)Cl was the most effective.

Emission Characteristics of a Navistar 7.3L Turbodiesel Fueled with Blends of Oxygenates and Diesel

Several oxygenates have been proposed and tested for use with or as diesel fuel. This paper examines two such oxygenates, CETANER and dimethyl ether (DME), partially or wholly produced by Air Products and Chemicals, Inc’s Liquid Phase Technology. In previous studies on a single cylinder compression ignition engine and a Volkswagen TDI four cylinder engine, significant reductions in particulate matter emissions were observed with blends of CETANER in diesel fuel. In this study, experiments were performed on a multicylinder Navistar 7.3L Turbodiesel engine confirmed and extended the observations from the earlier studies. This is an important step in not only showing that the fuel does perform on each type of engine in similar fashion, but also in showing that DME and its derivatives can give consistent, significant results in lowering emissions. The oxygenated fuels were blended to achieve a net addition of 2 wt.% oxygen in the blended fuel. A pressurized fueling system was developed to deliver mixtures of DME-diesel at up to 1 MPa (150 psi). With the DME-diesel blend, less consistent emissions results were obtained owing to an inability to sufficiently the fuel in the rail.

REACTIONS OF ETHYLIDENE DIACETATE : FORMATION OF N-VINYLAMIDE PRECURSORS ETHYLIDENE BISACETAMIDE AND ETHYLIDENE BISFORMAMIDE

Abstract Ethylidene diacetate ( EDA ) reacts with formamide or acetamide under stoichiometric base or catalytic Lewis acid conditions to afford the corresponding ethylidene bisamides and N-vinylamides. Sn(OAc) 2 afforded an overall 82.6% selectivity to the desired acetamide derivatives. Sn(OAc) 2 and Zn(OAc) 2 facilitate amide attack at the tertiary carbon of EDA .