No abstract

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 microns in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 microns in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM2.5 samples than in the PM2.5+ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO4, while most of the V spectra closely resembled that of vanadyl sulfate (VO.SO4.xH2O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsenate (As+5). X-ray diffraction patterns of the PM2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM2.5 fraction and from 88 to 97% for the PM2.5+ fraction. Based on 13C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.

Diethyl carbonate (DEC) has been produced by the oxidative carbonylation of ethanol in the gas phase over a heterogeneous CuCl2/PdCl2 catalyst supported on activated carbon. Yields of DEC with this catalyst are approximately 10 wt % with the byproducts diethoxymethane, ethyl formate, and acetaldehyde also formed in significantly lower yields. Treatment of the catalyst immediately after preparation with potassium hydroxide enhances the production of DEC almost 2-fold without increasing the amount of byproducts formed. The reactions that form DEC and the byproducts occur in a parallel, rather than a sequential, manner indicating that it should be possible to identify a catalyst which is more selective for DEC.

The thermal decomposition of white birch wood and filter pulp was studied in water and methanol vapor at 2 MPa pressure in a flow-through reactor. The abundance of the volatile products was monitored by on-line GC/MS using repetitive sampling in combination with fast separation on a short capillary column. The reactor was heated to 400 °C at 20 °C/min and the intensity profile of the product ions within the 30−200 amu range recorded. The system was capable of separating the profiles of typical hemicellulose products evolved at lower temperature from the characteristic cellulose and lignin products detected from wood. Char yields in methanol were similar to those in an inert gas atmosphere; however, the presence of water markedly increased the amount of char produced. The product distribution of cellulose was strongly affected by the solvents. In methanol, pyran derivatives dominate besides levoglucosan and glycolaldehyde, whereas the relative abundance of 2-furaldehyde and 5-(hydroxymethyl)-2-furaldehyde increased in the presence of water. Water catalysis was also indicated by lowering the decomposition temperatures of cellulose. High-pressure (6.5 MPa) thermogravimetric experiments in helium or hydrogen atmospheres were also found to lower the reaction temperature of wood. This observation can be explained by the catalytic effect of reaction water released during the thermal decomposition of wood.

No abstract