Research into the chemical composition of refinery slag from silicon production for its efficient recycling

The aim was to investigate the chemical composition of refinery slag obtained during silicon production in order to identify approaches to its further recycling. Research samples were collected from the slag remained after oxidation refining at the JSC Silicon (AO Kremny), RUSAL (Shelekhov, Irkutsk Oblast). The methods of X-ray phase, X-ray fluorescence, metallographic and scanning electron microscopy were employed to investigate the chemical composition of the samples. It was found that the refinery slag under study includes such basic components as elemental silicon, its carbide and oxide, as well as elemental carbon. It was shown that silicon carbide is the product of incomplete reduction, resulting from melting silica-containing ores in a smelting furnace. According to the conducted X-ray fluorescent analysis, the samples also contain (wt %): Ca - 7.40; Al - 3.80; Fe - 0.30; Ba - 0.19; K - 0.14; Na - 0.09; Sr - 0.09; Mg - 0.08; Ti - 0.05; S - 0.02. Calcium and aluminium are present in the slag mostly in the form of oxides. Complex oxides of an anor-thite type were also found: CaO Al2O3 2SiO2. The refinery slag under study also features insignificant amounts of other metal oxides, which are released from the furnace slag forming during the smelting process. The slag produced by oxidation refining during crystalline silicon production is a technogenic raw material containing valuable components. Due to the significant content of silicon in the refinery slag (from 42% to 65%), the existing methods applied to recycle such an industrial material were analysed in terms of additional silicon extraction or production of commercial silicon-containing products, which are in demand in various industries.

Silicon clusters with six and seven unsubstituted vertices via a two-step reaction from elemental silicon

A synthetic shortcut to molecules that contain several unprotected silicon atoms comprising the whole range from localized to delocalized Si–Si bonds.

Transformative Si8R8 Siliconoids

Molecular silicon clusters with unsubstituted silicon vertices (siliconoids) have received attention as unsaturated silicon clusters and potential intermediates in the gas-phase deposition of elemental silicon. Investigation of behaviors of the siliconoids could contribute to the greater understanding of the transformation of silicon clusters as found in the chemical vapor deposition of elemental silicon. Herein we reported drastic transformation of a Si8R8 siliconoid to three novel silicon clusters under mild thermal conditions. Molecular structures of the obtained new clusters were determined by XRD analyses. Two clusters are siliconoids that have unsaturated silicon vertices adopting unusual geometries, and another one is a bis(disilene) which has two silicon–silicon double bonds interacted to each other through the central polyhedral silicon skeleton. The observed drastic transformation of silicon frameworks suggests that unsaturated molecular silicon clusters have a great potential to provide various molecular silicon clusters bearing unprecedented structures and properties.

Preparation, Analysis, and Degradation

Elemental silicon on which the entire technology is based is typically obtained by reduction of the mineral silica with carbon at high temperatures: . . . SiO2 + 2C → Si 2CO (2.1) . . . The silicon is then converted directly to tetrachlorosilane by the reaction . . . Si + 2Cl2 → SiCl4 (2.2) . . Tetrachlorosilane can be used to form an organosilane by the Grignard Reaction . . . SiCl4 + 2 RMgX → R2SiCl2 + 2 MgClX (2.3). . . This relatively complicatreaction has been replaced by the so-called Direct Process or Rochow Process, which starts from elemental silicon as is illustrated by the reaction . . . Si + 2 RCl → R2SiCl2 (2.4) . . . This process also yields RSiCl3 and R3SiCl, which­­ can be removed by distillation. Compounds of formula R2SiCl2 are extremely important as intermediates to a variety of substances having both organic and inorganic character. Hydrolysis gives dihydroxy structures, which can condense to give the basic [–SiR2O–] repeat unit. The nature of the product obtained depends greatly on the reaction conditions. Basic catalysts and higher temperatures favor higher molecular weight linear polymers. Acidic catalysts tend to produce cyclic small molecules or low molecular weight polymers. The hydrolysis approach to polysiloxane synthesis has been largely replaced by ring-opening polymerization of organosilicon cyclic trimers and tetramers, with ionic initiation. These cyclic monomers are produced by the hydrolysis of dimethyldichlorosilane. Under the right conditions, at least 50 wt % of the products are cyclic oligomers. The desired cyclic species are separated from the mixture for use in ring-opening polymerizations such as those described in the following section. In addition, “click” chemistry has been developed for new synthesis techniques in general, and polymerizations in particular. These approaches have been used to prepare polysiloxane elastomers and polydimethylsiloxane (PDMS) copolymers that can function as thermoplastic elastomers. New synthetic strategies for structured silicones, based on B(C6F5)3 have also been developed. Another new approach involves enzymes, such as the lipase enzymatically catalyzed synthesis of silicone aromatic polyesters and silicone aromatic polyamides.

A soluble molecular variant of the semiconducting silicondiselenide

Silicondiselenide is a semiconductor and exists as an insoluble polymer (SiSe2)nwhich is prepared by reacting elemental silicon with selenium powder in the temperature range of 400–850 °C.