PROJECT REPORT ON FUSED SALT SOLUTION ELECTROLYSIS

Submitted by: Vaibhav Kaushal, 10118092, MT-4 Metallurgy and Material Engineering

Introduction:
Electrolysis is the passage of a direct electric current through an ionic substance that is either molten or dissolved in a suitable solvent, resulting in chemical reactions at the electrodes and separation of materials. The main components required to achieve electrolysis are :

An electrolyte : a substance containing free ions which are the carriers of electric current in the electrolyte. If the ions are not mobile, as in a solid salt then electrolysis cannot occur. A direct current (DC) supply : provides the energy necessary to create or discharge the ions in the electrolyte. Electric current is carried by electrons in the external circuit. Two electrodes : an electrical conductor which provides the physical interface between the electrical circuit providing the energy and the electrolyte Each electrode attracts ions that are of the opposite charge. Positively charged ions (cations) move towards the electron-providing (negative) cathode, whereas negatively charged ions (anions) move towards the positive anode.

Faradays First law of electrolysis:

Michael Faraday reported that the quantity of elements separated by passing an electric current through a molten or dissolved salt is proportional to the quantity of electric charge passed through the circuit. This became the basis of the first law of electrolysis: m=k*q

Faradays Second law of electrolysis:

Faraday also discovered that the mass of the resulting separated elements is directly proportional to the atomic masses of the elements when an appropriate integral divisor is applied. This provided strong evidence that discrete particles of matter exist as parts of the atoms of elements.

Fused salt solution electrolysis:

Fused salt electrolysis is another electrometallurgical process whereby the valuable metal has been dissolved into a molten salt which acts as the electrolyte, and the valuable metal collects on the cathode of the cell. The fused salt electrolysis process is conducted at temperatures sufficient to keep both the electrolyte and the metal being produced in the molten state. Principally, the electrolysis of molten salts is very similar to electrolysis from aqueous solutions. However, there are significant differences.

Factors affecting the fused salt solution Electrolysis:

Decrease in the current efficiency during electro winning from fused salts is often observed and attributed to the following factors: Evaporation of the product of electrolysis. In order to reduce the evaporation of the products of the electrolysis, the process is usually carried out at lowest possible temperatures. At too low temperatures, the metal disperses in the melt and is unfavourable for accumulation whereas, at too high temperature the metal has an even high reactivity its loss thus increases and so does salt due to evaporation. Appearance of secondary reactions. The appearance of secondary reactions can be avoided sing proper cell and proper electrode material, operation conditions, electrolyte composition and cell construction. e.g. decreasing the contacting area between the metal and molten salt. Dissolution of metals in fused salts. The metal should be properly dispersed in to molten state i.e. it should dissociate into ions. An appropriate increase in current density can result in a more negative cathode potential, and favour the discharge of metal by reducing the relative loss of the metal and increasing the current efficiency. The current density at cathode determines the relative speed of metal dissolution and discharge. If the current density is too high, the metal reduction increase and the cathode zone or the overall fused salt can be overheated.

Dissolution of anodic products in the fused salts Anode effect: It occurs when terminal voltage increases rapidly and the current density decreases sharply. The electrolyte seems to be cut off from the anode by a layer of gas, and fine coronas due to spark discharge also appear around the anode.

Applications:
Many metals can be produced by electro winning from fusions of their salts-sodium, potassium, beryllium, aluminium and magnesium.

The HallHroult process: Extraction of Aluminium

The HallHroult process is used for extraction of Aluminium. Aluminium cannot be produced by the electrolysis of an aluminium salt dissolved in water because of the high reactivity of aluminium with the protons of water and the subsequent formation of hydrogen. As, in an aqueous solution, protons (H+) are preferentially reduced to atomic hydrogen before Al3+ ions, the reduction of Al3+ is done by electrolysis of a molten aluminium salt. This is a water free medium, and hence, H+ reduction is avoided.

Raw Material: The raw material for production of Aluminium is Anhydrous alpha Alumina, Al2O3. This is white, non-hygroscopic powder produced precipitated Al(OH)3is calcined at 1000 C.

The Cell or Pot: It consists of a rectangular steel cell about 8 feet long, 5 feet wide and 2 feet deep and it has a carbon lining which is backed by thermal insulation. A metal collector plate is buried in the carbon lining to conduct the current. The entire carbon lining is the cathode. Carbon anodes are attached to metal rods which hang from the superstructure. Carbon anodes are oxidized and consumed and they must be replenished at regular intervals. The anodes are made up of a mixture of high grade petroleum, coke, tar pitch and used electrode scraps. The materials are crushed, blended and shaped in hydraulic presses & then the green electrodes are heated or baked and the metal supporting rods are attached.

Electrolyte: The electrolyte is molten cryolite, Na3AlF6(sodium hexafluoroaluminate), called a "cell", this is remarkably stable compound and will dissolve about 20 percent Al2O3 Aluminium oxide has a melting point of over 2,000 C while pure cryolite has a melting point of 1,012 C. With a small percentage of alumina dissolved in it, cryolite has a melting point of about 1,000 C. Some aluminium fluoride, AlF3 is also added into the process to reduce the melting point of the cryolite-alumina mixture.

Electrolysis: The molten mixture of cryolite, alumina, aluminium fluoride is then electrolyzed by passing a direct electric current through it. The electrochemical reaction causes liquid aluminium metal to be deposited at the cathode as a precipitate, while the oxygen from the alumina combines with carbon from the anode to produce carbon dioxide, CO2. An electric potential of 3 to 5 Volts is needed to drive the reaction, and the rate of production is proportional to the electric current. An industrial-scale smelter typically consumes hundreds of thousands of Amperes for each cell. Cathode: AlF63- + 3 e = Al + 6 FAnode: 2 Al2OF62- + C(s) + 12 F- = + 4 AlF63- + CO2 + 4 e Overall cell reaction: 2 Al2O3 + 3 C = 4 Al + 3 CO2

The oxidation of the carbon anode reduces the required voltage across each cell, increasing the electrical efficiency, at a cost of continually replacing the carbon electrodes with new ones, and also the cost of releasing carbon dioxide into the atmosphere. The cells are electrically heated to reach the operating temperature with this current, and the anode regulator system varies the current passing through the cell by raising or lowering the anodes and changing the cell's resistance. The liquid aluminium is taken out with the help of a siphon operating with a vacuum, in order to avoid having to use extremely high temperature valves and pumps. The liquid aluminium then may be transferred in batches or via a continuous hot flow line to a location where it is cast into aluminium ingots. The aluminium can either be cast into the form of final cast-aluminium products, or the ingots can be sent elsewhere such as a rolling mill to be pressed into sheets, or a wire-drawing mill producing aluminium wires and cables. While solid cryolite is denser than solid aluminium at room temperature, the liquid aluminium product is denser than the molten cryolite at temperatures around 1,000

C (1,830 F), and the aluminium sinks to the bottom of the electrolytic cell, where it is periodically collected.] The tops and sides of the cells are covered with layers of solid cryolite which also act as thermal insulation. The unavoidable electric resistance within each cell produces sufficient heat to keep the cryolite-alumina mixture molten. The electrolysis process produces exhaust which escapes into the fume hood and is evacuated. The exhaust is primarily CO2 produced from the anode consumption and hydrogen fluoride (HF) from the cryolite and flux. HF is a highly corrosive and toxic gas, even etching glass surfaces. The gases are either treated or vented into the atmosphere; the former involving neutralization of the HF to its sodium salt, sodium fluoride.

Extraction of Magnesium:
Magnesium is produced by the electrolysis of a molten solution of magnesium, sodium and other chlorides. Raw Material: The magnesium Chloride required is prepared from seawater in the following way: The Mg2+ cation is the second most abundant cation in seawater (occurring at about 12% of the mass of sodium there), . To extract the magnesium, calcium hydroxide is added to seawater to form magnesium hydroxide precipitate. MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 Magnesium hydroxide (brucite) is insoluble in water so it can be filtered out, and reacted with hydrochloric acid to obtain concentrated magnesium chloride. Mg(OH)2 + 2 HCl MgCl2 + 2 H2O The obtained magnesium chloride aftr evaporating is the hydrated chloride, MgCl2 .6H2O. This cannot be completely dehydrated by heating alone, because some of the hydrogen of the water combines with chlorine to form HCland leave a residue of MgO. The MgO is then briquetted with carbon and eposed to a current of chlorine gas in an electrically heated shaft furnance. MgO + C + Cl2 MgCl2 + CO The Cell: The electrolytic cell is a steel shell about 16 feet long, 5 feet wide and 6 feet deep. Electrolyte: The electrolyte contains about 60 percent NaCl, 15 percent CaCl2 and 25 percent MgCl2. It is maintained at a temperature of 700 to 750C by controlled fire underneath the cell. Electrolysis: The voltage may be from 5 to 8 volts and the cell can take from 30,000 to 70,00 amperes. Magnesium is principally obtained by electrolysis of fused magnesium chloride from brines,

wells, and sea water. At the cathode, the Mg2+ion is reduced by two electrons to magnesium metal: Mg2+ + 2 e Mg Metallic Magnesium is lighter than electrolyte and is collected on the top of the bath. The Magnesim is liberated at the bottom and sides of the steel shell and the droplets of metal breakaway and rise to the top of the bath.

At the anode, each pair of Cl ions is oxidized to chlorine gas, releasing two electrons to complete the circuit: 2 Cl Cl2 (g) + 2 e Chlorine gas, HCl, and oxygen are liberated at the anode and the gases are led off to the acid plant where chlorine is converted to HCl for re-use.

Electrolysis of Magnesium