Monitoring of pyrometallurgical processes

Abstract: The concentration of an element in a molten metallurgical phase (3) is measured by applying an electrical potential across two electrodes (1, 2) separated by a solid electrolyte (7) containing cations of the element to be measured immersed in the melt, and measuring the current flowing between them. The solid electrolyte is preferably of β-alumina or zirconium silicate or phosphate.

Description: This invention relates to the monitoring of pyrometallurgical processes, and more particularly to the measurement of concentrations of major metallic species in molten metallurgical phases such as slags, mattes, bullions and impure or semi-refined molten metals. It is already known to use electrolytic sensors in which a reference electrode is separated by a solid electrolyte from an electrode immersed in a melt and an e.m.f. is measured, to study the concentration trend of a minor element in the melt. Such a procedure is described for example in UK patent no. GB-A-1,470,558. One of the disadvantages associated with the use of such sensors is that the e.m.f. change is the same for a change from 1 part per million to 10 parts per million of the element being detected as it is for the change from 10,000 to 100,000 p.p.m. Such devices are therefore considerably less sensitive at higher concentrations of the element being detected. We have now devised a method of monitoring the concentration of elements in metallurgical melts that is appreciably more sensitive to changes in concentration than the method described above. Thus in one aspect the present invention provides a method of measuring the concentration of an element in a molten metallurgical phase, which comprises immersing in said phase two electrodes which are separated by a solid electrolyte containing cations of the element to be measured, applying an electrical potential across the electrodes, and measuring the current flowing between them as a measure of concentration of the element in the molten phase. Preferably the solid electrolyte is oxidic in character. More preferably the solid electrolyte is based on β-alumina or zirconium silicate or phosphate, with a mobile cation which is a cation of the element to be measured incorporated therein. The molten metallurgical phase is suitably a matte or impure molten metal. Preferably the solid electrolyte is in the form of a tube surrounded by means adapted to create a stagnant layer of melt around the electrolyte. The solid electrolyte should suitably be modified by partial substitution of its cationic content by cations of the element being detected, e.g. by means of immersion or electro-chemical exchange. Such a procedure is described in TRANS IMM.88 (1979) C229-233. The invention in another aspect provides apparatus for measuring the concentration of an element in a melt comprising two electrodes separated by a solid electrolyte made of β-alumina or zirconium silicate or zirconium phosphate containing cations of the element to be measured, a source of electrical potential to be applied across said electrodes, and means for measuring current flowing between the electrodes. The invention will be further described by way of example only, with reference to the accompanying drawing which shows in diagrammatic form an apparatus suitable for monitoring the copper content of a copper matte. As shown in the drawing, two electrodes 1 and 2 are used. Electrode 1 is immersed directly in a molten matte 3 while electrode 2 is in contact with copper 4 enclosed within a closed-ended tube 5 composed of layers of porous refractory (alumina) which is penetrated by the molten matte (as indicated by numeral 6a) and copper-substituted β-alumina, designated 6 and 7 respectively. An electrical potential is applied across electrodes 1 and 2 by means of battery or cell 8 and the current flow is monitored by means of ammeter 9. The current flowing is directly proportional to the diffusional flux of copper from within the matte to the surface of the solid electrolyte 7 through the matte held in the porous membrane, and therefore linearly dependent on the concentration of copper in the molten matte. The copper 4 provides good electrical contact between the electrode 2 and the solid electrolyte 7. The invention will be further illustrated with reference to the following experimental procedure. Molten lead and molten sodium were separated by a closed-ended ceramic tube made of N + /β-alumina. Iron wire electrodes were inserted into the molten lead (negative) and the molten sodium (positive). These wires were connected via a source of e.m.f., an ammeter and a voltmeter. Sodium was titrated through the ceramic tube into the lead and from the coulombs passed the concentration of sodium in lead was calculated. After each titration the system was allowed to equilibriate. A constant potential of 1 volt was then applied in the opposite direction so that sodium was transferred from the molten lead to the sodium reservoir. In this case the rate of transfer of sodium was controlled by diffusion of the sodium through the lead to the lead/β-alumina interface. As is shown in the following table the current, i.e. the rate of transfer of sodium, is a linear function of sodium concentration. APPLIED VOLTAGE (v) CONCENTRATION (wt%) Na in Pb CURRENT FLOWING (ma) 1.03 1.22 0.18 1.03 2.45 0.232 1.027 3.67 0.263 1.02 4.90 0.300 It should be noted that in this experiment the melt was stagnant. However in an agitated or mobile system a porous layer around the β-alumina tube would be required in order to ensure a stagnant layer around the probe. Alternatively the probe may comprise a pellet of the solid electrolyte sealed into a ceramic tube some distance from the end thereof so as to create a stagnant zone at the bottom of the tube.

Claims: A method of measuring the concentration of an element, in particular a metal, included in a molten metallurgical phase selected from slags, mattes, bullions, impure molten metals, semi-refined molten metals and alloys thereof, comprising: immersing a first electrical lead (1) in the molten phase (3), disposing a solid electrolyte matrix (7) in the said phase in spaced relationship to said first electrical lead, forming an electrical connection between a second electrical lead (2) and to the solid electrolyte matrix so that the solid electrolyte is between the said first and second electrical leads and separates the second electrical lead from the first electrical lead when the first electrical lead and the solid electrolyte matrix are disposed in the molten phase, and so that the second electrical lead (2) is surrounded by the element to be measured and enclosed by the solid electrolyte (7); characterized by providing means (6) adapted to produce a stagnant layer of the molten phase in electrical contact with the said solid electrolyte; applying an electrical potential across the said electrical leads; and measuring the current flowing between the electrical leads as a measure of the concentration of the said element in the said molten phase. A method as claimed in claim 1, characterized in that the solid electrolyte is oxidic in character. A method as claimed in claim 1 or 2, characterized in that the said solid electrolyte comprises a material selected from β-alumina, zirconium silicate and zirconium phosphate, with a mobile cation of the element to be measured included in said electrolyte. A method as claimed in any of claims 1 to 3, characterized in that the said element is copper, and the said molten phase is a copper matte. Apparatus for measuring the concentration of an element, in particular a metal, included in a molten metallurgical phase, comprising: a first electrical lead (1) to be immersed in the molten phase (3), a solid electrolyte matrix (7) to be disposed in the said phase in spaced relationship to the said first electrical lead, a second electrical lead (2) electrically connected to the solid electrolyte matrix so that the solid electrolyte is between the said first and second electrical leads and separates the second electrical lead from the first electrical lead when the first electrical lead and the solid electrolyte matrix are disposed in the molten phase, and wherein the second electrical lead (2) is surrounded by the element to be measured and enclosed by the solid electrolyte (7); characterized by means (6) adapted to produce a stagnant layer of the molten phase in electrical contact with the said solid electrolyte; a source (8) of electrical potential connected across the said electrical leads; and means (9) for measuring current flowing between the electrical leads as a measure of the concentration of the said element in the said molten phase. Apparatus as claimed in claim 5, characterized in that the solid electrolyte is oxidic in character. Apparatus as claimed in claim 5 or 6, characterized in that the said solid electrolyte is made of a material selected from β-alumina, zirconium silicate and zirconium phosphate and containing cations of the element to be measured. Apparatus as claimed in any of claims 5 to 7, characterized in that the said element is copper, and the said molten phase is a copper matte.

Inventors: FRAY DEREK JOHN, FRAY, DEREK JOHN
Applicants: MINERAL IND RES ORG, MINERAL INDUSTRY RESEARCH ORGANISATION
Application year: 1989
Main classification: G01N27
IPC codes: G01N27, G01N33