Downs process molten salts

Other Metals. AH the sodium metal produced comes from electrolysis of sodium chloride melts in Downs ceUs. The ceU consists of a cylindrical steel cathode separated from the graphite anode by a perforated steel diaphragm. Lithium is also produced by electrolysis of the chloride in a process similar to that used for sodium. The other alkaH and alkaHne-earth metals can be electrowon from molten chlorides, but thermochemical reduction is preferred commercially. The rare earths can also be electrowon but only the mixture known as mischmetal is prepared in tonnage quantity by electrochemical means. In addition, beryIHum and boron are produced by electrolysis on a commercial scale in the order of a few hundred t/yr. Processes have been developed for electrowinning titanium, tantalum, and niobium from molten salts. These metals, however, are obtained as a powdery deposit which is not easily separated from the electrolyte so that further purification is required. 

We have already described the refining of copper and the electrolytic extraction of aluminum, magnesium, and fluorine. Another important industrial application of electrolysis is the production of sodium metal by the Downs process, the electrolysis of molten rock salt (Fig. 12.15) ... 

The alkali metals are the most violently reactive of all the metals. They are too easily oxidized to be found in the free state in nature and cannot be extracted from their compounds by ordinary chemical reducing agents. The pure metals are obtained by electrolysis of their molten salts, as in the electrolytic Downs process (Section 12.13) or, in the case of potassium, by exposing molten potassium chloride to sodium vapor ... 

One synthesis approach that does not rely on CNT formation from the gas phase is molten salt synthesis. The reactor consists of a vertically oriented quartz tube that contains two graphite electrodes (i.e. anode is also the crucible) and is filled with ionic salts (e.g. LiCl or LiBr). An external furnace keeps the temperature at around 600 °C, which leads to the melting of the salt. Upon applying an electric field the ions penetrate and exfoliate the graphite cathode, producing graphene-type sheets that wrap up into CNTs on the cathode surface. Subsequently, the reactor is allowed to cool down, washed with water, and nanocarbon materials are extracted with toluene [83]. This process typically yields 20-30 % MWCNTs of low purity. 

In MSO processing, organic wastes are chemically broken down to carbon dioxide, nitrogen gas, and water vapor in a bath of molten salt. The salt may be of various compositions, with variable melting points. Inorganic materials react with the salt mixture, producing ash and salts for subsequent treatment or disposal. The oxidation takes place at lower temperatures than incineration or other combustion technologies. 

Sodium chloride is plentiful as rock salt, but the solid does not conduct electricity, because the ions are locked into place. Sodium chloride must be molten for electrolysis to occur. The electrodes in the cell are made of inert materials like carbon, and the cell is designed to keep the sodium and chlorine produced by the electrolysis out of contact with each other and away from air. In a modification of the Downs process, the electrolyte is an aqueous solution of sodium chloride. The products of this chloralkali process are chlorine and aqueous sodium hydroxide. 

Alkali metals are produced commercially by reduction of their chloride salts, although the exact procedure differs for each element. Both lithium metal and sodium metal are produced by electrolysis, a process in which an electric current is passed through the molten salt. The details of the process won t be discussed until Sections 18.11 and 18.12, but the fundamental idea is simply to use electrical energy to break down an ionic compound into its elements. A high reaction temperature is necessary to keep the salt liquid. 

The use of ionic liquids (also called molten or fused salts) as reaction media is a relatively new area, although molten conditions have been well established in industrial processes (e.g. the Downs process. Figure 10.1) for many years. While some molten salts are hot as the term suggests, others operate at ambient temperatures and the term ionic Uquids is more appropriate. This section provides only a brief introduction to an area which has implications for green chemistry (see Box 8.3). 

Manufacturing processes in which metals are extracted from molten metal salts are important examples of the uses of molten salts and include the Downs process, and the production of Li by electrolysis of molten LiCl, and of Be and Ca from BeCl2 and CaCl2, respectively. 

The first, and now obsolete, industrial processes for producing raw sodium metal were based on the carbon reduction of sodium carbonate or sodium hydroxide. The first industrial production of pure sodium metal was performed by molten-salt electrolysis of the pure sodium hydroxide, NaOH, in so-caUed Castner cells. Most modern processes for the production of sodium now involve molten-salt electrolysis of highly pure sodium chloride. Actually, since 1921, when the process was invented by J.C. Downs, the electrolysis has been performed in Downs electrolytic cells at the DuPont de Nemours Canadian facilities at Niagara Falls, Ontario, Canada. The electrolytic cell consists of four cylindrical anodes made of graphite surrounded at the bottom of the cell by steel cathodes, and a fine steel mesh acts as a separator between anodic and cathodic compartments. Each cell contains a batch of 8 tonnes of a molten-salt mixture with the following chemical composition NaCl (28 wt.%), CaCl (26 wL%), and BaClj (46 wt.%). 

The term eutectic is commonly encotmtered in molten salt systems. The reason for forming a eutectic mixture is to provide a molten system at a convenient working temperature. For example, the melting point of NaCl is 1073 K, but is lowered if CaCl2 is added as in the Downs process. 

Another factor, unique to MSRs, down rates this reactor in comparison with other liquid-cooled reactors in terms of isolation. In an MSR, the fuel is dissolved in the molten salt. The fission process produces tritium, the radioactive form of H2. This places an additional requirement on the intermediate heat transfer loop to ensure that tritium does not reach the H2 production facility. Significant work has been conducted to develop methods to ensure tritium does not cross the heat exchanger. Most of this work is associated with development of fusion reactors that have very large tritium inventories. It is unclear how serious this issue is. 

Sodium is produced by an electrolytic process, similar to the other alkali earth metals. (See figure 4.1). The difference is the electrolyte, which is molten sodium chloride (NaCl, common table salt). A high temperature is required to melt the salt, allowing the sodium cations to collect at the cathode as liquid metallic sodium, while the chlorine anions are liberated as chlorine gas at the anode 2NaCl (salt) + electrolysis —> Cl T (gas) + 2Na (sodium metal). The commercial electrolytic process is referred to as a Downs cell, and at temperatures over 800°C, the liquid sodium metal is drained off as it is produced at the cathode. After chlorine, sodium is the most abundant element found in solution in seawater. 

In a number of processes the plastics prior to pyrolysis are dissolved into product oil for example, so that the viscosity is quite controllable. Other options, though today somewhat obsolete, are the use of a molten lead, tin or salt bath. Unfortunately, residues accumulate on top of this bath, and periodic shut-down for cleaning is inevitable. The process has been used commercially for PMMA. 

---