Determination of chlorine and bromine in automotive shredder residues by oxygen bomb and ion chromatography
An analytical procedure, oxygen bomb combustion-ion chromatography (IC), has been developed for the determination of total chlorine in Automotive Shredder Residues (ASR). Samples of these residues are fired under elevated oxygen pressure (30 atm) and the combustion products are transferred into a Na2 CO3/NaHCO3 absorbent solution containing 1% of H2 O2; the chlorine contents are then evaluated by ion chromatography. The use of the non-suppressed IC determination with a conductivity detector provides a rapid, sensitive and selective method for chlorine determination in ASR, allowing determinations of this heteroatom at levels below 1% in the presence of bromine and sulfur. Moreover, the proposed method allows the simultaneous determination of chlorine, bromine and sulfur which are potential environmental hazards.
Chlorine characterization and thermal behavior in MSW and RDF.
Chlorine, as a key element causing high temperature corrosion and low efficiency in waste-to-energy plants, and its thermal behavior has widely drawn attention. In this study, the chlorine content in eight fractions of municipal solid waste (MSW) was quantified and characterized using five analytical methods. The influence of the operating temperature, and fuel additives like sulfur and silica on the volatilization of chlorine in combustion process was also investigated. The results showed: these fractions cover a wide range of chlorine content from 0.1 wt.% in wood to >6 wt.% in non-packaging plastics (dry basis). Polyvinylchloride (PVC) from packaging, electrical wire insulation etc. in plastics and chloride salts (mainly NaCl) in kitchen waste are the main sources of organic and inorganic chlorine. The increase of the operating temperature from 700 degrees C to 1000 degrees C has more influence on the HCl formation for kitchen waste than that for PVC. Sulfur addition leads to 20-40% higher HCl formation rate in most fractions. Silica supports the chlorine release at relatively low temperatures between 700 degrees C and 850 degrees C. These findings enhance to understand the thermal behavior of chlorine in MSW and RDF (refuse derived fuel) in waste-to-energy plants and lead to the suggestions for a fuel management for waste derived fuels in order to avoid chlorine induced corrosion.
The crystal structure of stilpnomelane. Part II. The full cell
Summary The structural formula of stilpnomelane averaged from 37 representative literature analyses and based on the determined structure is (Ca,Na,K)4(Ti0·1Al2·3Fe35·5Mn0·8Mg9·3)[Si63Al9](O,OH)216·nH2O. Ferrostilpnomelanes have up to 12 R 3+ cations in the octahedral sheet, ferristilpnomelanes commonly have between 24 and 30 R 3+ cations, rarely up to 37. The two groups can be distinguished by accurate X-ray powder diffraction, ferrostilpnomelanes having d 001 less and a greater than have ferristilpnomelanes. The unit cell is triclinic, a = b∼21·8 Å, γ = 120°, d 001∼12·2 Å, P . Hexagonal groups or ‘islands’ of 24 silicon-oxygen tetrahedra co-ordinate to the octahedral sheet, the centres of the ‘islands’ are displaced by 5a/12, 8b/12 on either side of the octahedral sheet as a result of warping of this sheet to permit articulation with the smaller tetrahedral sheet. The 24-tetrahedra ‘islands’ are linked laterally by 6-member rings of inverted tetrahedra, which in turn link at their apices to like rings connecting the next sheet of ‘islands’. Thus a single tetrahedral layer is 4 tetrahedra thick and has symmetry 6/m. The 6-member rings of tetrahedra act as hinges permitting up to 0·5 Å extension or contraction of the tetrahedral sheet to accommodate variations in the octahedral sheet dimensions with varying R 2+/R 3+ ratio.