WO2004072636A1 - Measuring rate of change of oxygen concentration and intrinsic oxidation rate in a pile of material - Google Patents

Measuring rate of change of oxygen concentration and intrinsic oxidation rate in a pile of material Download PDF

Info

Publication number
WO2004072636A1
WO2004072636A1 PCT/AU2004/000151 AU2004000151W WO2004072636A1 WO 2004072636 A1 WO2004072636 A1 WO 2004072636A1 AU 2004000151 W AU2004000151 W AU 2004000151W WO 2004072636 A1 WO2004072636 A1 WO 2004072636A1
Authority
WO
WIPO (PCT)
Prior art keywords
pile
oxygen concentration
probes
gas
change
Prior art date
Application number
PCT/AU2004/000151
Other languages
French (fr)
Other versions
WO2004072636A9 (en
Inventor
John William Bennett
Yury A. Stepanyants
Alistair Ian Maxwell Ritchie
Original Assignee
Australian Nuclear Science & Technology Organisation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Australian Nuclear Science & Technology Organisation filed Critical Australian Nuclear Science & Technology Organisation
Priority to AU2004210879A priority Critical patent/AU2004210879A1/en
Publication of WO2004072636A1 publication Critical patent/WO2004072636A1/en
Publication of WO2004072636A9 publication Critical patent/WO2004072636A9/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention relates to methods and systems for measuring rates of change in oxygen concentration and for measuring intrinsic oxidation rates in a pile of material. In one form, it relates to a method for measuring in situ the rate of change in oxygen concentration and intrinsic oxidation rate in the pile.
  • the use of biooxidation and bioleach piles in which the operating conditions of the piles are closely controlled is a recent innovation in the mining industry.
  • the piles are typically used to brea down sulfidic minerals in refractory gold ores so as to improve the amount of gold extracted in subsequent processing, or to release metals into lixivants ihiough the oxidation cf the oulfidic minerals.
  • the conventional technology relating to the use of biooxidation and bioleach piles in the processing of minerals relies primarily on indicators such as iron concentration and 30 microbial population in runoff water, which are external to the pile, in order to monitor progress of oxidation of materials within the pile and to determine optimal operational .
  • a disadvantage of the use of such external indicators is that there is a significant time lag between changes in the oxidation processes in the pile and changes in the external indicators.
  • a further disadvantage of the conventional technology is that the use of external indicators can only provide a measure of overall pile performance but can not provide information about the spatial distribution of oxidation rates within the pile. There is, therefore, a need for technology that can provide information on the spatial distribution of oxidation rates within a pile.
  • the authors measure an oxygen gradient within the oxygen diffusion zone (less than 1 metre) near the surface of the pile of material, and derive the relative oxidizability of materials in the pile from the oxygen flux associated with that gradient. Since the method relies on the oxygen gradient near the surface of the pile, it is not capable of providing information on oxidation rates deep within the pile.
  • a further disadvantage is that it can not provide an accurate spatial distribution of oxidation rates within a pile.
  • Still another disadvantage is that it can provide only relative rates of oxidation, based on the determined oxygen flux. These may be useful in comparing different waste piles, but can not be used effectively to predict rates of production of pollutants.
  • this method is only applicable to waste mineral piles, and not to biooxidation and bioleach piles, since the forced aeration that is practised in biooxidation and bioleach piles would disrupt the oxygen gradient that is central to the method.
  • a method of determining a rate of change in a gaseous oxygen concentration within a pile of material, said pile of material comprising both solid phase and gas phase and optionally liquid phase comprising the steps of:
  • the altering may comprise passing a gas containing oxygen through the at least a part of the pile.
  • the method may additionally compose the step of deteraiining an intrinsic oxidation rale (IOR) at the at least one location in the pile.
  • IOR intrinsic oxidation rale
  • S Q is an approximate value of the IOR
  • is the volume fraction of the gas phase in the pile of oxidisable material
  • p'"(0) is the intrinsic gas density of the gas at the location in the pile at which the
  • IOR is determined, immediately after the altering of the gaseous oxygen concentration therein.
  • the concentration of oxygen in the gas containing oxygen may be sufficient to
  • the method may comprise the steps of aerating at least a part of the pile of material and of ceasing the aeration before the step of measuring the gaseous oxygen concentration.
  • the step of measuring may comprise the steps of :
  • the method may additionally comprise recording the time at which each of the i s steps of measuring is performed.
  • the step of altering comprises forming a cavity in the pile of m.iteriul ⁇ ueh ihaf the oxygen content of the ga phase in S'-ud m ⁇ y and in the surrounding region i? fuhsianii.-dly ihe rarne & • -> the or- gen conce ⁇ tr-iiou in the ambieni v 'nmo.i heie outside iht pile ol material, A pr ⁇ be for measuring o " gen ma;, be inserted into the cavity.
  • the rate of change of oxygen concentration is measured a plurality of times, and the change with time in at least one of the IOR and the rate of 25 change of oxygen concentration is used to estimate at least one of:
  • a method of determining a spatial distribution of rates of change of gaseous oxygen concentration within a pile of material, said pile of material comprising both solid phase and gas phase and optionally liquid phase comprising the steps of:
  • step (iii) measuring an oxygen concentration in the gas surrounding the at least two of the probes in the pile; (iv) determining a rate of change in oxygen concentration of the gas surrounding the at least two of the probes in the pile wherein the determining comprises measuring the oxygen concentration in the gas surrounding at least two of the probes after the altering of step (ii) has been stopped; and (v) determining a spatial distribution of rates of change in gaseous oxygen concentration in the pile.
  • the altering may comprise passing a gas containing oxygen through the locations oi the at least tv/o ol the probes.
  • the method may additionally comprise the step of determining H spatial distribution of lOPs v-dlhin the pile.
  • ibere is provided method of cot it rolling I lie opeialing • .o ⁇ dt oiu* of a ⁇ tle oi material taid pile of m «*»leri il comprising both solid phase and ⁇ JS ph t c and optionally liquid ph ⁇ de compi k-ing:
  • the step of adjusting may comprise a process selected from the group consisting of aerating at least one portion of the pile and contacting at least one portion of the pile of material with a liquid selected from the group consisting of water and an aqueous liquid.
  • a method for constructing, and controlling the operating conditions of, a pile of material comprising both solid phase and gas phase and optionally liquid phase, comprising: (i) determining at least one property of the material; (ii) using the at least one property in a model to determine a value of at least one parameter of construction of the pile of material; (iii) constructing the pile using the value of the at least one parameter of construction; (iv) determining information selected from the group consisting of an IOR of oxidisable material in the pile and a spatial distribution of IORs of oxidisable material in the pile; and (v) adjusting the operating conditions of the pile.
  • the at least one property of the material may be selected from the group consisting of porosity, gas permeability, sulfur content, IOR, and a combination of these.
  • the model may be a computer model based on a deterministic formulation of multiphase flow through porous media.
  • the step of adjusting may include a process selected from the group consisting of aerating the pile and contacting the pile of material with a liquid selected from the group consisting of water and an aqueous liquid.
  • Ln a fifth aspect of the invention there L provided a system for determining a rate of change in a gaseous oxygen concentration within of a pile ⁇ i material, said pile of mat em 1 ⁇ omprring both solid pha ⁇ e and gas phase* and optionally liquid phr « e, said -. d cm comprising: ti) means fur dtering the giw»!i ⁇ - •» / gen (.oiiccnnaiioii in at l ⁇ t * r. ⁇ oi i pile (ii) means for measuring the gaseous oxygen concentration within the pile of material; (iii) means for repeating the measuring of the gaseous oxygen concentration within the pile of material;
  • the means for altering may comprise for example an aerator such as a gas vent or a gas outlet, and may comprise means for passing a gas containing oxygen through the at least part of the pile, for example an aerator such as a gas vent or a gas outlet, and means for stopping the passing, for example a valve.
  • the valve is commonly fitted to the means for passing a gas.
  • the system may further comprise:
  • the means for determining the time may be for example a data logger or a timing device.
  • the means for determining an intrinsic oxidation rate may be for example a computer or other calculating device.
  • the means for altering may comprise for ex-uuple at least one asialor such ⁇ gas * ent oi J gri utlet id may tump ⁇ se mean ior pasoiug J gi com nntug o ygen founded ⁇ udi the location ot the n lo t h* •» l die ⁇ o
  • ⁇ le ci one c i- comm nly inicd t th; means lot pj- ⁇ ing * g s 1 he system may additionally comprise means for determining a spatial distribution of IORS within the pile for example a computer or other calculating device
  • more than one probe is connected to a particular means for measuring and there is additionally means lo selectively direct gas from a probe connected thereto to the particular means for measuring at any particular time.
  • the means to selectively direct gas may comprise one or more valves, and may also comprise a controller for controlling the valve(s).
  • a system for controlling the operating conditions of a pile of material comprising: (i) means for determining information selected from an IOR of oxidisable material in the pile and a spatial distribution of IORs in the pile; and (ii) means for adjusting at least one operating condition of the pile.
  • the means for determining information may conveniently comprise for example a
  • the means for adjusting may comprise means selected from the group consisting of means for aerating the pile, for example an aerator, and means for contacting the pile of material with a liquid selected from the group consisting of water and an aqueous liquid, for example an irrigator.
  • the system may comprise a computer, lo and the means for determining may comprise a computer.
  • the means for adjusting may be capable of adjusting the operating conditions selectively in different portions of the pile.
  • Figure 1 a is a diagrammatic representation of a aste rock pile showing positions of a plurality of holes, in cadi of vhich are Inc eJ ptohe-. for mea mmg o ygen concentrat ion, ⁇ nd optionally -.o oiher p-.rainete ⁇ in accordance *vjth ( he mcihon ol iii. pre s ent im emioir .
  • Figw e lb is a cltagiammaiic reprcsemauuii oi a bioo-Jd ⁇ iion/bioleaeh pile, shoving positions of a plurality of strings of probes for measuring oxygen concentration, and optionally also other parameters, means for supplying air and water to the pile and a computer for controlling the above components;
  • Figure lc is a diagrammatic representation of a biooxidation/bioleach pile that has 25 been constructed in two stages, showing two sets of strings of probes for measuring oxygen concentration, and optionally also other parameters, means for supplying air to the pile and a computer for controlling the above components;
  • Figure 2 is a diagrammatic representation of the drilling of a hole in a waste rock pile using a drill which injects air into the heap, for example a rotary percussion air blast, 30 for providing holes for the insertion of probes in the pile and for modifying the concentration of oxygen in a region surrounding the hole, using the method in accordance with the second embodiment of the invention
  • Figure 3 is a diagrammatic representation of a hole in a waste rock pile, showing two groups of probes at different depths capable of measuring oxygen concentration, temperature and another parameter, the connection of the oxygen probe tubes to an oxygen sensor, the connections of the probes to a computer and the backfill used to seal the hole;
  • Figure 4a is a graph representing the change in oxygen concentration over time within two different uniformly aerated biooxidation/bioleach piles, which have different rates of oxygen consumption wherein the results are obtained from a plurality of probes within each pile;
  • Figure 4b is a graph representing the change in oxygen concentration over time as a function of depth for 3 different sizes of the aeration zone in a waste rock pile represented in Figure la;
  • Figure 5a is a graph representing the change in the relative deviation of the approximate IOR trorn its more precise value (as determined by Equation 1), o»er time, at differenl points vitliin a bioo idation/bioleach pile corresponding to the o.-ygen concentration curves, foi Pile 1 in Figure 4a;
  • Figme c »b is a guph re pre cent inc (l e ch&nge in the relative deviation of the ippio imaie IuP- lioi ⁇ its moie p ⁇ co : alue (a_. determined by Hqinuoii l k '» ?r ittue J: a £Hiieiio ⁇ i depth for " > difi ⁇ mt se ot rh . ⁇ .noc ⁇ in u z «»nc c art s oiHing to the oxygen concentration curves in Figure 4b; and
  • Figure 6 shows the dependence of the IOR (as a proportion of the maximum IOR) as a function of the oxygen concentration (as a proportion of atmospheric oxygen concentration).
  • the IOR(s) and/or the rate(s) of change of oxygen concentration may be used to estimate one or more of the rate of conversion of metal substances in the pile to at least one metal substance from which the metal is recoverable, the amount of recoverable metal in the pile and the rate of production of pollutants in the pile.
  • the metal substances may be metal compounds, metal salts, metal complexes, organometallic compounds, metals or other metal substances.
  • the IOR(s) and/or the rate(s) of change of oxygen concentration may be used to estimate one or more of the rate of conversion of metal substances in the pile to at least one metal substance from which the metal is extractable.
  • the part of the pile in which gaseous oxygen concentration is altered in the method of determining a rate of change of oxygen concentration may comprise a contiguous part 5 of the pile or it may comprise a collection of unconnected portions or it may comprise the entire pile.
  • the gas containing oxygen may be air, oxygen or a mixture of oxygen and one or more other gases, the other gases being for example nitrogen, helium, carbon dioxide etc.
  • the concentration of oxygen in the gas containing oxygen is greater than the oxygen lo concentration in gas in the pile prior to the altering, at the location(s) where the measuring is performed.
  • the concentration of oxygen in the gas containing oxygen may be greater than about 5% on a weight, volume or mole basis, or greater than about 10, 15, 20, 30, 50, 50, 60, 60, 80 or 90%, or between about 100% and about 5%, or between about 50% and about 10% or between about 30% and aboul 15%, and may be about 5, 10, 15, 20 25, 30 40 50 60 70 GO °0 or 100% on ⁇ « eight volume or mole basis
  • the gas is an, and pieferably the altering of step (i) is sufficient to make the O' ygen conceuti ation in the ai lcdbi one Inc ilmu ⁇ hcie mc ⁇ GUiemenfs -tie nude appio -mutely equal lo the cu>nc * . ⁇ i ⁇ i id ⁇ u >»i o yseii in an he "r. ⁇ ot mc r ⁇ i tii'j ga ;nu o _, -.
  • step of measuring gaseous oxygen concentration may be repeated one or more times prior to cessation of the altering of step (i).
  • the IOR(s) is/are are function of oxidisable material in the pile which causes the change in the gaseous oxygen concentration.
  • the IOR(s) is/are determined at the location(s) where steps (ii) and (iii) are carried out in the pile.
  • the IOR So(( ⁇ o, &s, T) is 30 frequently described by the Monod formula:
  • the factor A (T) is a smooth function of temperature equalling unity at relatively low temperatures, T ⁇ 40°C. Examples of piles of oxidisable materials include biooxidation piles, bioleach piles, waste rock dumps and the like. Whereas the present invention is intended primarily for use in the mining industry, it may also be used in other industries, for e x ample food and agriculture, or other industries m which piles of oxidisable materials occur
  • the gaseous 0"» ygen coitcentiation may be expressed as any one of the following a p ⁇ iccnt ige bs- d on weight a percentage ba. e on volume mole fnelion mass fraction.
  • the rate of change in gaseous oxygen concentration may be conveniently be determined by any one of the following means:
  • An equation may be used to calculate the IOR in the region adjacent to the probe.
  • the following equation may be used to calculate an approximate value of the IOR of oxidisable material in the pile:
  • IOR is detemiined, immediately after the altering of the gaseous oxygen concentration therein.
  • Equation 2 may be derived from mass balance equations for the total gas phase (Equation 3a) .md for the o"ygen density Equation 3b):
  • v g is an intrinsic pore gas velocity
  • p g is a pore gas bulk density
  • Do is the effective diffusion coefficient of oxygen in the porous medium; by assuming that diffusion of oxygen within the pile is insignificant. This assumption may be valid in the period shortly after the gas in the at least part of the pile has been altered.
  • the rate of change of oxygen concentration, and optionally also the IOR is measured a plurality of times.
  • the change with time in one or both of the IOR and the rate of change of oxygen concentration may be used to estimate one or more of:
  • the measurements may be made sufficiently frequently and at sufficient time intervals to allow the estimates of (a), (b) and/or (c) to be made, but preferably not so frequently as to interfere unduly with the operation of the pile.
  • the time interval between lo measurements may be for example between about 4 and 40 days, or between 5 and 35 days or between 6 and 30 days or between 7 and 25 days or between 8 and 20 days or between 10 and 15 days, and maybe about 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35 or 40 days
  • the effeeli 'e lifetime of a pile may commonly be about 6 months for a bi " idation pile.
  • measurements may be made between 2 md 40 times or between is 3 and 35 or between 4 and 30 or between 5 and 25 or between 5 and 20 times, and may be made about 2, 3 4, 5 o, 7, l. c » 10 l c > 20 25 3d, 35 m -10 time-
  • An estimate of the l l line or ⁇ be Stamm »>'.. ⁇ 1 by ;- rr pohling n; or more oi the 10T a the rate ol change oi o _, ecu toj icc t ⁇ r nto , and ti ⁇ i ⁇ i , iimc d ⁇ ch > p rnctil r p.n ,M , j .
  • the invention also provides a method of determining a spatial distribution of rates of change in gaseous oxygen concentration within a pile of material. Insertion of a plurality of probes into the pile may be accomplished by either locating the probes during building of the pile of material, or inserting probes into holes cut in the pile.
  • the plurality 25 of probes may be arranged in a predetermined array. The distribution of probes is commonly dictated by convenience and cost. hi the case that probes are inserted into holes drilled into the pile, there may be a plurality of probes inserted into each of the holes at different depths in order to provide information about the spatial distribution of conditions within the pile.
  • the probes may be inserted into the pile in connected groups ("strings") which may be inserted at an angle to the vertical, the angle being dictated by convenience in the lo construction of the pile.
  • strings a plurality of the strings is inserted into a pile, each of which would commonly be no closer than 0.5 metre to another such string.
  • the pile is constructed.
  • the second part of the pile may be on top of the first part, or it may be beside the first part or it may be in some other location relative to the first part. It will be further understood that the pile may have more than two parts, and may have for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more than 10 parts, each of which may be constructed with a
  • the probe may be capable of measuring the concentration of oxygen in the gas phase in the region adjacent to the probe.
  • the probe(s) may also be capable of 30 measuring the temperature of the pile of material in the region surrounding the probe.
  • the probe(s) may also be capable of measuring one or more other parameters of interest in managing the pile of material, for example gas permeability and gas pressure.
  • separate probes may be provided to determine temperature and/or the one or more other parameters.
  • the probe capable of measuring temperature is a thermocouple or a thermistor.
  • the probe for measuring another parameter of interest may be a manometer.
  • the period of time over which the measurements are made may be any period from about 1 hour to several days (eg 1 to 5 days or 1 to 3 days or 1 day) or even weeks.
  • the time period is preferably less than about 15 hours or less than 12 hours or less than 10 hours.
  • the time period may be in the range of 1 to 15 hours, 1 to 14 hours, 1 to 13 hours, 1 to 12 hours or 1 to 10 hours.
  • the time period may be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 hours. More preferably, the measurements are made over a period in the range of from about 1 to about 5 hours.
  • this may help to ensure that the determination of the IOR causes as little as possible disruption to the operation of the piles, and may enable calculation of the IOR to be made sufficiently rapidly so as to permit effective control of the operational conditions of the pile of material hi lhe case of waste mineral dump piles, this may enable rapid classification of the dumps based on the measured IOP or distribution of the IORs.
  • the method may include a step in which the calculated IOP. is used to make decisions concerning operation of the pile.
  • data relating lo other parameters of the pile, for example temperature are also used in making said decisions.
  • the decisions relate to adjusting the operating conditions of the pile of material. More preferably the decisions relate to improving the operating conditions of the pile of material.
  • the step of adjusting may include aerating the pile and/or contacting the pile of material with water or aqueous liquid.
  • the pile may be aerated and/or contacted with water or an aqueous liquid at a rate sufficient to improve the oxidation rate of the pile of material.
  • the step of adjusting may also include using other methods to affect the oxidation rate of the pile of material.
  • aerating and/or contacting with water or aqueous containing liquid are at a rate sufficient to optimise the oxidation rate of the pile of material.
  • the oxidation rate may be a rate of biooxidation of sulfur-containing materials in the pile.
  • the calculated IOR or a distribution thereof may be used for computer modelling or simulation of the operation of the pile of material, in order to determine the effect of specific conditions on the operation of the pile of material.
  • the method includes the step of aerating the pile of material and lo then ceasing the aeration before the measurement of oxygen concentration is made or before the first of two or more measurements of oxygen concentration is made, in order to provide a gaseous oxygen concentration in the pile of material that is approximately homogeneous and is higher than the gaseous oxygen concentration before the aerating.
  • the oxygen concent ration within the pile may be altered using or a is mixture oi gases, said mi '.tine containing oxygen.
  • the oxygen concentration in the mb ture of gases is greater than the oxygen concentration in the gas in the pile prior to the altering ai the location ⁇ ) where the measurements are made.
  • the or each probe is inserted into a cavity in the pile of material that has been aerated such that the oxygen content of the gas phase in the cavity and in the surrounding region is substantially the same as the oxygen concentration in the ambient atmosphere outside the pile of material.
  • the region preferably has a radius of greater than
  • This embodiment may provide an initial level of oxygen in the region surrounding the probe that is similar to the level in the atmosphere outside the pile of material.
  • the oxygen concentration in the cavity and the region surrounding the cavity may be altered before the measurement of oxygen concentration, using oxygen or a
  • the cavity into which the probe is inserted is formed using a drill that passes air, oxygen or a mixture of gases, said mixture containing oxygen, into the cavity as the drilling progresses.
  • the cavity may be a hole that has been drilled in the pile.
  • the cavity or hole may be sealed or closed after the probe(s) is (are) appropriately located therein. The sealing or closing is conveniently achieved by backfilling the cavity or hole.
  • the time elapsed after aeration of the pile of material and the distance of the probe from the surface of the pile of material are such that the diffusion of oxygen from the outside of the pile of material to the probe is not significant.
  • equation (2) provides an acceptable estimate of the actual IOR, by satisfying the assumption that diffusion of oxygen from outside the pile into interstitial voids is insignificant.
  • the condition for ensuring that this assumption is satisfied is given by:
  • / is the distance of the probe from the surface of the pile
  • the method iccording lo due first embodiment of the present invention offers the
  • a computer model may be used to determine at least one parameter of construction of the pile.
  • the model may be based on a deterministic formulation of multiphase flow through porous media, for example a computer model as described in Australian Patent No. 6083790, the contents of which are incorporated herein by reference, or a computer model similar to that model.
  • the calculated IOR optionally together with other data gathered from the same or a different probe(s), may be used for computer modelling or simulation of the operation of the pile of material, in order to determine the effect of specific conditions on the operation of the pile of material.
  • the means for measuring the gaseous oxygen concentration may comprise a tube through which a sample of the gas to be measured is conveyed to a sensor capable of measuring oxygen concentration.
  • a sensor capable of measuring oxygen concentration.
  • each tube may be connected to a separate oxygen sensor, or one or more of the oxygen sensors may be connected to a plurality of tubes.
  • There may additionally be means to control from where in the pile the sample of gas was taken.
  • the means to control may comprise a plurality of valves linked to a means to control the valves, for example a computer.
  • the plurality of prob s may be arranged within the pile in a predetermined array.
  • the r wyeiu ma > include, meaii-"* tor n ine. i 1*- .a one »d the c dud 'fed I f _, tht ' i _ ic ii c uie ih . don nd die l i tiprr irnre m m il ; eu mr * nc .
  • a system for controlling the operation of a pile of material comprising:
  • (iii) means to determine (a) rate(s) of oxidation of material within the pile
  • (iv) means to determine the IOR or a spatial distribution of the IOR within the pile; (v) means to determine temperature and optionally a spatial distribution of temperature within the pile; (vi) means for controlling the provision of the one or more materials to the pile.
  • the system may include means for coupling the probes of (i) to the means to determine of (iii) and (v).
  • the one or more materials in (vi) may be air or other gas, water or other aqueous liquid, for example.
  • the means of (iii), (iv) and (v) may include a computer.
  • the means of (vi) may be a computer linked to means for providing air or other gas to the pile and/or means for contacting one or more portions of the pile of material with water or aqueous liquid.
  • the probe(s) maybe capable of measuring gaseous oxygen concentration, and optionally they may also be capable of measuring temperature, and optionally also other parameters of relevance to the operation of the pile of material.
  • separate probes for measuring gaseous oxygen concentration, temperature and optionally the other parameters may be located close to each other in a group.
  • the numbei of probes will depend on the she of the pile and the chosen distance between piobes. In particular there may be between 2 and 50 or more of the probes or groups of probes within the pile.
  • the means for providing air or other gas to the pile may be capable of providing the air or other gas selectively to different portions of the pile at different rates.
  • the means for providing water or other aqueous liquid to the pile may be capable of providing the water or other aqueous liquid to different portions of the pile at different rates.
  • the system may also include means for adjusting other parameters of relevance to the operation of the pile in response to the determined IOR or spatial distribution of the IOR in the pile.
  • the means for determining the IOR or a spatial distribution of the IOR may be a computer.
  • the means for controlling the provision of air or other gas and of water or other aqueous liquid to the pile may comprise a series of valves connected to the computer.
  • the means for controlling the provision of air or other gas and/or water or other aqueous liquid to the pile may comprise means to control the provision of the air or other gas and the water or other aqueous liquid selectively to different portions of the pile at different rates.
  • the oxygen concentration, u (x , y , t), in the gas phase in the pore space of a heap of sulfidic material may be calculated using:
  • Equation 5 may thus be written as: 1 ⁇ ⁇ g_ whilsSi-O s
  • Equation 6 shows that, in order to achieve a high oxidation rate at all points in a pile of sulfidic material, the second term in the square brackets must be much smaller than the first.
  • the specific gas discharge rate, ⁇ g v g should be much greater than D 0 /h.
  • the latter term is commonly about 5 x 10 "7 m/s.
  • This value of specific discharge rate is readily achievable in practice. It can be shown that for the oxidation rate throughout the heap to be near the maximum value, the specific discharge rate should be about 10 "4 m/s.
  • the gas discharge rate should be high enough for the second term in Equation 6 to balance the third term. Such discharge rates can be achieved by providing air to the base of the pile. The pressures required are quite modest
  • the multiplier outside the square brackets may commonly be about 5 ⁇ 10 " ⁇ .
  • the intrinsic ooxxiiddsation rate should be high, for example about 5 x 10 " kg
  • Waste rock dumps are typically much higher than bioheaps, commonly being up to 25m or more, but the oxidation rate of the sulfidic material is typically much lower, commonly about lx 10 "8 kg (O 2 ) m “3 s "1 .
  • the multiplier at about 7x10 is still greater than
  • Collections of probes 112, 114 and 116 comprise groups of probes at different depths within the holes 102, 104 and 106. This is shown in greater detail in Figure 3.
  • the probes of collections 112, 114 and 116 are located sufficiently far from the surface of the pile thai diffusion of oxygen from outside the pile is negligible during the period of a measurement. Although this depends on a number of factors (Equation 4) a typical minimum distance to the surface of the pile may be about 0.5 to 1 metre.
  • Collections of probes 112, 114 and 116 (which include collections of tubes 152, 154 and 156) send electrical data to computer 140 by means of collections of electrical cables 122, 124 and 126 and send gas samples to oxygen detectors 142, 144 and 146 by means of collections of tubes (probes) 152, 154 and 156.
  • certain types of probe for example thermistors, require a device such as a signal transducer, to convert a signal from the probe to a signal suitable as input for a computer. It will be understood that such devices, although not shown in the Figures, are in fact present when necessary.
  • Oxygen detectors 142, 144 and 146 are also connected to collections of electrical cables 122, 124 and 126 and transmit data through them to computer 140. Alternatively, signals maybe sent from collections of probes 112, 114 and 116 and oxygen sensors 142, 144 and 146 to the computer 140 by means of
  • 5 transmitters or other convenient method there may be more than three or less than three oxygen detectors connected to collections of oxygen tubes 152, 154 and 156.
  • oxygen detectors there may be 1, 2, 4 , 5 or 6 or more oxygen detectors.
  • air is provided to the holes as shown in Figure 2 (for a typical hole 215). This creates a zone of aeration 235 in which the oxygen concentration is o approximately the same as in the outside atmosphere.
  • the holes are sealed by backfilling with backfills 132, 134 and 136, and data acquisition from collections of probes 112, 114 and 116 is commenced.
  • the data acquired over a period of approximately 10 to 12 hours is sent to the computer 140 which then determines a rateof change in o"* ygen concentration for each o" ygen probe.
  • Fiom that and Irom othei data the computer 140 can then determine a spatial distribution of the IOP and optionally also of other paiarnelers
  • ⁇ w data may be stored in the compiler for subsequent offline nnalysr Tlnr dfcniafiv*; in i be commonly t &l in the of » ⁇ -. - ie ⁇ ucl ⁇ tle r
  • the pipes are fitted with air ilov/ contiol 'ab e 252, 254 and 256, which are connected to computer 220 by cables 262, 264 and 266.
  • signals may be sent from the computer 220 to the valves 252, 254 and 256 by means of a transmitter or other convenient method.
  • Rock is then laid on top of pipes 242, 244 and 5 246 to form pile 201.
  • Strings of probes 202 including tubes 223, 225, 227), 204 (including tubes 229, 231 and 233) and 206 (including tubes 235, 237 and 239) are located in pile 201 as it is being constructed.
  • Strings of probes 202, 204 and 206 contain individual groups of probes 222 (including tube 223), 224 (including tube 225), 226 (including tube 227), 228 (including tube 229), 230 (including tube 231), 232 (including 0 tube 233), 234 (including tube 235), 236 (including tube 237) and 238 (including tube 239).
  • Each of these groups of probes contain individual probes which are capable of measuring gaseous oxygen concentration, and optionally temperature and/or other parameters relevant to the operation of the pile.
  • the strings of probes in Figure lb are each similar to the collection of probes shown diagrammatically in Figure 3, although they are located at an angle in the pile, and are located in the material of pile 201 rather than being located in a backfilled hole.
  • the groups of probes 222, 224, 226, 228, 230, 232, 234, 236 and 238 are located sufficiently far from the surface of the pile that diffusion of oxygen from outside the pile is negligible during the period of the measurement. Although this depends on a number of factors (Equation 4) a typical minimum distance to the surface of the pile may be about 0.5 to 1 metre.
  • Probes 223, 225, 227, 229, 231, 233, 235, 237 and 239 within groups 222, 224, 226, 228, 230, 232, 234, 236 and 238 respectively are designed to measure oxygen concentration and comprise a tube for conveying air samples to oxygen detectors 247, 248 and 249.
  • oxygen detectors there may be more than three or less than three oxygen detectors connected to collections of oxygen tubes 223, 225, 227, 229, 231, 233, 235, 237 and 239.
  • the oxygen detectors are located externally to pile 201. This is shown in greater detail in Figure 3.
  • Groups of electrical cables 212, 214 and 216 transmit data from probes 202, 204 and 206 and from detectors 247, 248 and 24--* to computer 220.
  • dal may be sent to the computer 220 by means of a tiansmitier or other convenient method, stater pipes 272, 274 and 276 are located on oi abo .c ihe top of pil 01.
  • h lch *n pipe- * 272 274 md 176 may ha . e one or oie outlet " ⁇ IOL ⁇ -/ i .i ( l i ilij j t tl ' ii r ⁇ b ⁇ oii f ⁇ h pin.. 272 2? J id 27? > tn » ' hi conuol led b* •* i - ⁇ 2.
  • air Prior to determining the IOR or a spatial distribution of the IORs, air is passed through pipes 242, 244 and 246 in order to provide oxygen to the parts of the pile in which probes 223, 225, 227, 229, 231, 233, 235, 237 and 239 are located, such that the oxygen concentrations at those locations are approximately the same as the oxygen concentration in the atmosphere outside the pile.
  • the air flow through pipes 242, 244 and 246 is then stopped by closing valves 252, 254 and 256. These valves remain closed throughout the period in which data is acquired for determining the IOR or a spatial distribution of the IORs.
  • air flow may be controlled by turning on or off blowers, fans or other means for providing the air to pipes 242, 244 and 246.
  • a measurement of oxygen concentration is made by each of the probes in the pile, using detectors 247, 248 and 249 to measure the oxygen concentration of samples of gas taken by probes 223, 225, 227, 229, 231, 233, 235, 237 and 239.
  • measurements of temperature and any other desired parameters are made by detectors in strings of probes 202, 203 and 204.
  • the data so acquired is sent to the computer 220 by means of groups of cables 212, 214 and 216. Measurements of oxygen concentration, temperature and optionally other parameters are then made at a number of times over a period of approximately 10 hours. Data from these measurements are transmitted to the computer 220.
  • the computer then processes that data to determine the IOR or a spatial distribution of the IORs, and optionally also other operating conditions of pile 201 or spatial distributions of the other conditions. It may then determine what changes need to be made to the operating conditions of pile 201 to improve its operation.
  • the computer may then send signals to valves 252, 254, 256, 282, 284 and 286, and optionally to other devices capable of influencing the operating conditions of all or part of pile 201 shadow in such a way as to impro /e the opera ling conditions in al! or part of the pile 201.
  • pile 405 compiises first part 407. with strings 410, 412 md -1 14 and s con pan 40", « th siring* 4 i d 41.J and 420.
  • ⁇ ir pipe: 430 432 aid 434 ic l ⁇ t en brio « n ⁇ i p n 4 5 ⁇ « ⁇ r >tin _ r Hi ⁇ p in 405 md n pi ⁇ e 4 " o 43 md 440 ) ⁇ c !• i. r-.d b. lo ' ihe ci a i, ⁇ -
  • air pipes 430, 432 and 434, fitted with valves 450, 452 and 454 and cables 480, 482, and 484 are initially laid on the site of the pile.
  • strings 410, 412 and 414, connected to computer 470 by collection of cables 422 are incorporated in pile 405.
  • air pipes 436, 438 and 440, fitted with valves 456, 458 and 460 and cables 486, 488 and 490 are laid on or in the top of first part 407.
  • strings 416, 418 and 420, connected to computer 470 by collection of cables 427 are incorporated in second part 409.
  • IOR of the pile may be determined in a manner similar to that described for Fig. lb. IOR, or a distribution of IORs, may be determined separately for first part 407 and for second part 409, or it may be determined for pile 405 as a whole.
  • the pile is initially aerated through air pipes 430, 432, 434, 436, 438 and 440, by opening valves 450, 452, 454, 456, 458 and 460, under control from computer 470 via cables 480, 482, 484,486, 488 and 490, and subsequently the valves are closed to stop the aeration.
  • a measurement of oxygen concentration is made by each of the probes strings 410, 412, 414, 416, 418 and 420, using detectors 415 and 425 in to measure the oxygen concentration.
  • the data so acquired is sent to computer 470 by means of cables 490 and 492 Measurements of c ygen concentration, temperature and optionally other parameters are then made al a number of limes over a period of appro imately 10 hours. Data from these measurement-, are transmitted to the computer 470. The computer then processes that data to determine a spatial distribution oi the IOP -,
  • Hi H i" " i ll ' •_ > ⁇ >_ I air may move tln ⁇ ugli ihe porous material ol pile 205a as shown by ie an j in Figure 2, such that the aerated region 235a has an oxygen concentration approximately equal to that of ambient air.
  • the radius of aeration is represented by the radial distance from the hole to the boundary of the aerated region. In order to provide sufficient lime over the length of a 10 hour measurement of the IOR, the radius of aeration should be preferably at least 5 metres.
  • Figure 3 shows a diagrammatic representation of one of the holes 102, 104 and 106 of Figure la, containing probes and backfill 340. As noted previously, this shares many features in common with the strings of probes 202, 204 and 206 of Figure lb.
  • a plurality of probes is inserted into hole 350, which is located in pile 301.
  • the probes are organised in groups of probes 352 and 354 which are located at different depths within hole 350.
  • Each of groups 352 and 354 comprise probes for measuring gaseous oxygen concentration (302 and 304), temperature (306 and 308) and another relevant parameter (310 and 312).
  • Probes 306, 308, 310 and 312 are connected to computer 320 by electrical cables 326, 328, 330 and 332.
  • Oxygen concentration probes 302 and 304 comprise tubes 322 and 324 which can transmit samples of gas from the vicinity of groups 352 and 354 to an oxygen detector 318, which is conveniently located outside the pile.
  • Oxygen detector 318 comprises pumps 314 and 316, which pump gas samples from tubes 322 and 324 to the oxygen sensor 319 located within detector 318.
  • Valves 315 and 317 (controlled by computer 320 using a means not shown here for reasons of simplicity) select which of the probes is in service at a particular time.
  • Signals from oxygen sensor 318 are transmitted to computer 320 using electrical cable 323, or using a transmitter or similar convenient means.
  • Temperature probes 306 and 308 are preferably thermistors or thermocouples.
  • Figure 4a shows the dependency of oxygen concentration upon time within a biooxidation/bioleach pile for two different examples of the operational conditions of the pile (pile 1 and pile 2) as obtained from numerical modelling.
  • Figure 5a shows the dependency on time of rhc relative deviation r of (he approximate value of the JOP- from iis tnoi e previse ⁇ lue > ' > ' te c ⁇ faed fro E uaa on 1 );
  • Equation 2 The estimated value of the IOP, obtained using Equation 2, agrees well with the more precise value from Equation 1 if the measurements of oxygen concentration are conducted within several hours of cessation of aeration of the pile and within the bulk of the pile. Typically for a biooxidation/bioleach pile, measurements would commence immediately following the cessation of aeration, or alternatively one or more measurements may be made before the cessation.
  • the condition for determining the minimum distance of probes from the surface of the pile is given by Equation 4. These conditions serve to ensure that diffusion of oxygen from outside the pile is minimal during the period of the measurement. Curves 5, 9, 11, 10 and 1 in Figure 4a correspond to locations which are close to the pile surface, and consequently which violate the conditions described above.
  • the other curves, 2-4 and 6-8, correspond to locations within the bulk of the pile.
  • the time period within which reliable measurements may be obtained depends on the location of probes from which the measurements are taken. Consequently in Figure 4a, the locations within the pile corresponding to curves 5, 9, 11, 10 and 1 have oxygen concentrations that are higher than would be expected from Equation 2, since the oxygen at those locations has been augmented by oxygen diffusing from outside the pile.
  • Figure 5 a shows that the deviation of the calculated IOR from exact value of the IOR increases with time, as the greater time periods allow more oxygen to diffuse from outside the pile to the location(s) of the probe(s).
  • Curves 2-4 and 6-8 do not show these deviations from the theoretical values since the locations of the probes are sufficiently far from the surface of the pile that the amount of oxygen that can diffuse to those locations over the time of the test is insignificant.
  • Figure 4b illustrates the dependency of oxygen concentration upon time as a function of depth and of size of the aerated region, as obtained from numerical modelling of a waste rock pile such as that shown diagrammatically in Figure la.
  • Figure 5b shows the deviation of the calculated oxygen concentrations of Figure 4b from the more precise values obtained from Equation 1 hi Figure 4b and Figure 5b dal a is shown for 5 different depths within a 20 metre deep pile- curves 1 to 5 represent dat al distances of 1 0 5.5 10 o.
  • the relative deviation of the IOR at 1 metre depth, shown in Figure 5 is less than for the deeper locations, since the diffusion of oxygen from outside the pile partially offsets the depletion of oxygen due to the small size of the oxygen reservoir, hi the case of a 5 metre radius of aeration, location 5, near the surface, shows a slight positive relative deviation after some time, since the depletion is small due to a larger region of aeration, and diffusion from outside the pile more than compensates for it.
  • Figure 6 shows a graph of the normalised IOR as a function of normalised oxygen concentration as described by the Monod formula (Equation 1).
  • This graph describes the behaviour of the IOR when the actual material being tested is the same. It shows that the IOR depends on oxygen concentration, so that when oxygen concentration is below the atmospheric level, the IOR will be lower than its maximum value. It further shows that the deviation of the IOR from its maximum value is relatively slight for higher values of oxygen concentration. For example, when oxygen concentration is only 50% of the atmospheric level, the IOR is over 90% of its maximum level. However at low levels of oxygen concentration, the change of the IOR in response to a relatively small change in oxygen concentration is much larger.

Abstract

The rate of change of gaseous oxygen concentration, in a pile of material such as a bioleach pile or a waste rock pile (201), is determined at one or more locations (222, 224, 226, 228, 230, 232, 234, 236, 238) by adding oxygen gas to a region of the pile; and measuring the oxygen concentrations at the locations as they change over time. A spatial distribution of intrinsic oxidation rates may then be calculated, and the results used to control the operation of the pile via, for example, selective aeration (252, 254, 256) or irrigation (282, 284, 286).

Description

MEASUTH IG F-ATE OF CHANGE OF O Λ GEl I GUI ICEl 1 fiΛAIIOl ! Al to 11 IT1-JQ 1&1C -JLS A ΪIOI ' RATE in A PILE OF MATERIAL
Technical Field
5 The present invention relates to methods and systems for measuring rates of change in oxygen concentration and for measuring intrinsic oxidation rates in a pile of material. In one form, it relates to a method for measuring in situ the rate of change in oxygen concentration and intrinsic oxidation rate in the pile.
Background of the Invention lo The use of biooxidation and bioleach piles in which the operating conditions of the piles are closely controlled is a recent innovation in the mining industry. The piles are typically used to brea down sulfidic minerals in refractory gold ores so as to improve the amount of gold extracted in subsequent processing, or to release metals into lixivants ihiough the oxidation cf the oulfidic minerals. It is important in the operation of Iheεe i: pi lee to optimise the o idaliυn nles in th pile in order to optimise i e yield of m tric in the rite ol conversion of metal
Figure imgf000003_0001
in the pile to metal cubsiances irom which the metal u α*co»'Ciablc
Acid mine Hi --mage ( AJMD) i exulting Irom ιlι
Figure imgf000003_0002
se micurs in /ctεle rod piles gtner ited b thr mining industry * nnj r
Figure imgf000003_0003
'tι pioblrm f he pi blriiic *' ιh "f-'_fc '• iiueni .uπe / ui Jtiuυ-»plι.ικ. o n,n jam >u ... to sediment layers containing sulfides. The oxidation of sulfides produces a high groundwater sulfate concentration, a low pH and traces of metals such as nickel, copper, cobalt, zinc, lead and mercury. The pollutant concentrations in drainage depend mainly on the rate of pollutant generation in the waste sediments. There is a need for technology that
25 can measure in situ a rate of oxidation of the materials in a waste rock pile in a short period of time, so that decisions regarding classification and management of the pile can be made in a timely manner.
The conventional technology relating to the use of biooxidation and bioleach piles in the processing of minerals relies primarily on indicators such as iron concentration and 30 microbial population in runoff water, which are external to the pile, in order to monitor progress of oxidation of materials within the pile and to determine optimal operational . A disadvantage of the use of such external indicators is that there is a significant time lag between changes in the oxidation processes in the pile and changes in the external indicators. A further disadvantage of the conventional technology is that the use of external indicators can only provide a measure of overall pile performance but can not provide information about the spatial distribution of oxidation rates within the pile. There is, therefore, a need for technology that can provide information on the spatial distribution of oxidation rates within a pile. There is a further need for technology that can provide that information rapidly and repeatedly, so that changes to the operating conditions of the pile can be made in response to changes in the oxidation processes occurring in the pile in order to improve the operating efficiency of the pile.
Conventional technology relating to both biooxidation/bioleach piles and waste rock piles may alternatively or additionally rely on the determination of the oxidation rate of materials based on the use of laboratory instruments to estimate oxidation of the oxidisable material in the pile, using small samples from a pile. A disadvantage of these laboratory determinations, however, is that they cannot provide real-time information on conditions within a pile at a particular location and time. A further disadvantage of laboratory measurement of oxidation rales is ihat sampling from the pile in ord=r to conduct laboratory-based amlysic may interfere with the operation of the pile and may also affect die z unple o taken in ό manner thai πli ?rε ύs o^ idaiion rate.
A lediiiit l p.iper by Elbsihng n «'/ U loi.Uc Hydrology, 2-J 1 or-'3 323-3?/,) deτπl? r a method f«n c im uιn rc iive o nl oinu i -iføc of no »ι;πalc in '* v ufe uimei ή pile by me- iiing υ - -ti com-cinr iiion 'lthm ihe pile s -i Junction oi depth. 1 hit method however does not use deliberately oxygenation of the measurement site, but instead relies on diffusion of oxygen from outside the pile. In doing so, the authors measure an oxygen gradient within the oxygen diffusion zone (less than 1 metre) near the surface of the pile of material, and derive the relative oxidizability of materials in the pile from the oxygen flux associated with that gradient. Since the method relies on the oxygen gradient near the surface of the pile, it is not capable of providing information on oxidation rates deep within the pile. A further disadvantage is that it can not provide an accurate spatial distribution of oxidation rates within a pile. Still another disadvantage is that it can provide only relative rates of oxidation, based on the determined oxygen flux. These may be useful in comparing different waste piles, but can not be used effectively to predict rates of production of pollutants. Yet another disadvantage is that this method is only applicable to waste mineral piles, and not to biooxidation and bioleach piles, since the forced aeration that is practised in biooxidation and bioleach piles would disrupt the oxygen gradient that is central to the method.
Object of the Invention
It is an object of the present invention to overcome or substantially ameliorate at least one of the above disadvantages. Another object is to address some or all of the aforementioned needs.
Summary of the Invention
In a first aspect of the invention there is provided a method of determining a rate of change in a gaseous oxygen concentration within a pile of material, said pile of material comprising both solid phase and gas phase and optionally liquid phase, comprising the steps of:
(i) altering the gaseous oxygen concentration in at least a part of the pile of material; (ii) measuring the gaseouc o -j en concentiation in at least one location within that part of the pile of mater l altered by ihe gdc containing o- ygen, (m) repeating the tneα-uπng *" Jiit flcient nuinbsi of tune: at (he kas-i unt location iυ etuhfe deicπninauou •»! * ntz ot dunge m the f^α e>"»u L' ._» e.n M -. uιι "liυn di.stm die
Figure imgf000005_0002
(t) i ". ea.cd *n
Figure imgf000005_0001
pimr τo (hr upeatmg, -md
(iv) determining the rate of change in the gaseous oxygen concentration in the at least one location. The altering may comprise passing a gas containing oxygen through the at least a part of the pile. The method may additionally compose the step of deteraiining an intrinsic oxidation rale (IOR) at the at least one location in the pile. The equation:
Figure imgf000005_0003
may be used to calculate an approximate value of the IOR of oxidisable material in the pile, wherein:
SQ is an approximate value of the IOR; ε is the volume fraction of the gas phase in the pile of oxidisable material; and p'"(0) is the intrinsic gas density of the gas at the location in the pile at which the
IOR is determined, immediately after the altering of the gaseous oxygen concentration therein.
The concentration of oxygen in the gas containing oxygen may be sufficient to
5 make the oxygen concentration in the at least one location approximately equal to the concentration of oxygen in air. The method may comprise the steps of aerating at least a part of the pile of material and of ceasing the aeration before the step of measuring the gaseous oxygen concentration. The step of measuring may comprise the steps of :
(a) transferring a sample of gas from the region surrounding the probe to a location 10 external to the pile;
(b) passing the sample of gas to a device capable of measuring gaseous oxygen concentration; and
(c) using the device to measure a gaseous oxygen concentration of the sample of gas. The method may additionally comprise recording the time at which each of the i s steps of measuring is performed.
In on embodiment, the step of altering comprises forming a cavity in the pile of m.iteriul εueh ihaf the oxygen content of the ga phase in S'-ud m\y and in the surrounding region i? fuhsianii.-dly ihe rarne &-> the or- gen conceπtr-iiou in the ambieni v 'nmo.i heie outside iht pile ol material, A prυbe for measuring o" gen ma;, be inserted into the cavity.
In another embodiment, the rate of change of oxygen concentration is measured a plurality of times, and the change with time in at least one of the IOR and the rate of 25 change of oxygen concentration is used to estimate at least one of:
(i) a change in the rate of conversion of metal substances in the pile to metal substances from which the metal is recoverable, as a function of time, (ii) a change in the rate of production of pollutants in the pile as a function
30 of time, and
(iii) an effective lifetime of the pile.
In a second aspect of the invention there is provided a method of determining a spatial distribution of rates of change of gaseous oxygen concentration within a pile of material, said pile of material comprising both solid phase and gas phase and optionally liquid phase, comprising the steps of:
(i) locating a plurality of probes in the pile;
(ii) altering the gaseous oxygen concentration surrounding at least two of the probes;
(iii) measuring an oxygen concentration in the gas surrounding the at least two of the probes in the pile; (iv) determining a rate of change in oxygen concentration of the gas surrounding the at least two of the probes in the pile wherein the determining comprises measuring the oxygen concentration in the gas surrounding at least two of the probes after the altering of step (ii) has been stopped; and (v) determining a spatial distribution of rates of change in gaseous oxygen concentration in the pile. The altering may comprise passing a gas containing oxygen through the locations oi the at least tv/o ol the probes. The method may additionally comprise the step of determining H spatial distribution of lOPs v-dlhin the pile.
In a thhd aspect of the invention ibere is provided method of cot it rolling I lie opeialing .oπdt oiu* of a μtle oi material taid pile of m«*»leri il comprising both solid phase and ^JS ph t c and optionally liquid phαde compi k-ing:
(i) determining information selected from the group consisting of an IOR of oxidisable material in the pile and a spatial distribution of lORs of oxidisable material in the pile; and (ii) adjusting al least one operating condition of the pile.
The step of adjusting may comprise a process selected from the group consisting of aerating at least one portion of the pile and contacting at least one portion of the pile of material with a liquid selected from the group consisting of water and an aqueous liquid.
In a fourth aspect of the invention there is provided a method for constructing, and controlling the operating conditions of, a pile of material, said pile of material comprising both solid phase and gas phase and optionally liquid phase, comprising: (i) determining at least one property of the material; (ii) using the at least one property in a model to determine a value of at least one parameter of construction of the pile of material; (iii) constructing the pile using the value of the at least one parameter of construction; (iv) determining information selected from the group consisting of an IOR of oxidisable material in the pile and a spatial distribution of IORs of oxidisable material in the pile; and (v) adjusting the operating conditions of the pile.
The at least one property of the material may be selected from the group consisting of porosity, gas permeability, sulfur content, IOR, and a combination of these. The model may be a computer model based on a deterministic formulation of multiphase flow through porous media. The step of adjusting may include a process selected from the group consisting of aerating the pile and contacting the pile of material with a liquid selected from the group consisting of water and an aqueous liquid.
Ln a fifth aspect of the invention there L provided a system for determining a rate of change in a gaseous oxygen concentration within of a pile υi material, said pile of mat em 1 εomprring both solid phaεe and gas phase* and optionally liquid phr« e, said -. d cm comprising: ti) means fur dtering the giw»!i<- •» /gen (.oiiccnnaiioii in at l ^t * r.τπ oi i pile
Figure imgf000008_0001
(ii) means for measuring the gaseous oxygen concentration within the pile of material; (iii) means for repeating the measuring of the gaseous oxygen concentration within the pile of material;
(iv) means for determining the rate of change in the gaseous oxygen concentration.
The means for altering may comprise for example an aerator such as a gas vent or a gas outlet, and may comprise means for passing a gas containing oxygen through the at least part of the pile, for example an aerator such as a gas vent or a gas outlet, and means for stopping the passing, for example a valve. The valve is commonly fitted to the means for passing a gas. The system may further comprise:
(a) means for determining the time at which the measuring occurred; and
(b) means for determining an intrinsic oxidation rate at a location within the pile. The means for determining the time may be for example a data logger or a timing device. The means for determining an intrinsic oxidation rate may be for example a computer or other calculating device.
In a sixth aspect of the invention there is provided a system for determining a spatial distribution of rates of change in gaseous oxygen concentration within a pile of material, said pile of material comprising both solid phase and gas phase and optionally liquid phase, said system comprising:
(i) a plurality of probes capable of being located in the pile;
(ii) means for altering the gaseous oxygen concentration surrounding at least two of the probes;
(iii) means for measuring the gaseous oxygen concentration in the gas surrounding the at least two of the probes in the pile; (iv) means for determining the rate of change in gaseous oxygen concentration of the gas surrounding the at least two of the probes in the pile; and (v) means for determining a spatial distribution of lates oi change gaseous o" gen Loncentralion in the pile The means for altering may comprise for ex-uuple at least one asialor such ■ gas * ent oi J gri utlet id may tumpπse mean ior pasoiug J gi com nntug o ygen ihrυudi the location ot the n lo t h* •» l die ριo|χ for e "lup at le ft ιer tor udt > % g-t: s'tfiii oi -ι_, outlet πid m ^π., Is »ι stopping tin. -tll .ππg for z> t le u I'ast on.. » lve The Λ le ci one c i- comm nly inicd t th; means lot pj-ώing * g s 1 he system may additionally comprise means for determining a spatial distribution of IORS within the pile for example a computer or other calculating device
In one embodiment of the sixth aspect of the invention, more than one probe is connected to a particular means for measuring and there is additionally means lo selectively direct gas from a probe connected thereto to the particular means for measuring at any particular time. The means to selectively direct gas may comprise one or more valves, and may also comprise a controller for controlling the valve(s).
In a seventh aspect of the invention there is provided a system for controlling the operating conditions of a pile of material, said pile of material comprising both solid phase and gas phase and optionally liquid phase, comprising: (i) means for determining information selected from an IOR of oxidisable material in the pile and a spatial distribution of IORs in the pile; and (ii) means for adjusting at least one operating condition of the pile.
The means for determining information may conveniently comprise for example a
5 system according to the present invention for determining a rate of change of gaseous oxygen concentration The means for adjusting may comprise means selected from the group consisting of means for aerating the pile, for example an aerator, and means for contacting the pile of material with a liquid selected from the group consisting of water and an aqueous liquid, for example an irrigator. The system may comprise a computer, lo and the means for determining may comprise a computer. The means for adjusting may be capable of adjusting the operating conditions selectively in different portions of the pile.
Brief Description of the Drawings
Preferred forms of the present invention will now be described with reference to the is accompanying drawings therein:
Figure 1 a is a diagrammatic representation of a aste rock pile showing positions of a plurality of holes, in cadi of vhich are Inc eJ ptohe-. for mea mmg o ygen concentrat ion, <nd optionally -.o oiher p-.raineteπ in accordance *vjth (he mcihon ol iii. present im emioir . Figw e lb is a cltagiammaiic reprcsemauuii oi a bioo-Jdαiion/bioleaeh pile, shoving positions of a plurality of strings of probes for measuring oxygen concentration, and optionally also other parameters, means for supplying air and water to the pile and a computer for controlling the above components;
Figure lc is a diagrammatic representation of a biooxidation/bioleach pile that has 25 been constructed in two stages, showing two sets of strings of probes for measuring oxygen concentration, and optionally also other parameters, means for supplying air to the pile and a computer for controlling the above components;
Figure 2 is a diagrammatic representation of the drilling of a hole in a waste rock pile using a drill which injects air into the heap, for example a rotary percussion air blast, 30 for providing holes for the insertion of probes in the pile and for modifying the concentration of oxygen in a region surrounding the hole, using the method in accordance with the second embodiment of the invention; Figure 3 is a diagrammatic representation of a hole in a waste rock pile, showing two groups of probes at different depths capable of measuring oxygen concentration, temperature and another parameter, the connection of the oxygen probe tubes to an oxygen sensor, the connections of the probes to a computer and the backfill used to seal the hole;
Figure 4a is a graph representing the change in oxygen concentration over time within two different uniformly aerated biooxidation/bioleach piles, which have different rates of oxygen consumption wherein the results are obtained from a plurality of probes within each pile; Figure 4b is a graph representing the change in oxygen concentration over time as a function of depth for 3 different sizes of the aeration zone in a waste rock pile represented in Figure la;
Figure 5a is a graph representing the change in the relative deviation of the approximate IOR trorn its more precise value (as determined by Equation 1), o»er time, at differenl points vitliin a bioo idation/bioleach pile corresponding to the o.-ygen concentration curves, foi Pile 1 in Figure 4a;
Figme c»b is a guph re pre cent inc (l e ch&nge in the relative deviation of the ippio imaie IuP- lioiπ its moie p<co : alue (a_. determined by Hqinuoii l k '» ?r ittue J: a £Hiieiio<ι i depth for "> difiαmt se ot rh . ι.„ι in u z«»nc c art s oiHing to the oxygen concentration curves in Figure 4b; and
Figure 6 shows the dependence of the IOR (as a proportion of the maximum IOR) as a function of the oxygen concentration (as a proportion of atmospheric oxygen concentration).
Detailed Description of the In ention The IOR(s) and/or the rate(s) of change of oxygen concentration may be used to estimate one or more of the rate of conversion of metal substances in the pile to at least one metal substance from which the metal is recoverable, the amount of recoverable metal in the pile and the rate of production of pollutants in the pile. The metal substances may be metal compounds, metal salts, metal complexes, organometallic compounds, metals or other metal substances. The IOR(s) and/or the rate(s) of change of oxygen concentration may be used to estimate one or more of the rate of conversion of metal substances in the pile to at least one metal substance from which the metal is extractable.
The part of the pile in which gaseous oxygen concentration is altered in the method of determining a rate of change of oxygen concentration may comprise a contiguous part 5 of the pile or it may comprise a collection of unconnected portions or it may comprise the entire pile.
The gas containing oxygen may be air, oxygen or a mixture of oxygen and one or more other gases, the other gases being for example nitrogen, helium, carbon dioxide etc. The concentration of oxygen in the gas containing oxygen is greater than the oxygen lo concentration in gas in the pile prior to the altering, at the location(s) where the measuring is performed. The concentration of oxygen in the gas containing oxygen may be greater than about 5% on a weight, volume or mole basis, or greater than about 10, 15, 20, 30, 50, 50, 60, 60, 80 or 90%, or between about 100% and about 5%, or between about 50% and about 10% or between about 30% and aboul 15%, and may be about 5, 10, 15, 20 25, 30 40 50 60 70 GO °0 or 100% on ι « eight volume or mole basis Preierably the gas is an, and pieferably the altering of step (i) is sufficient to make the O' ygen conceuti ation in the ai lcdbi one Inc ilmu ~ hcie mc→GUiemenfs -tie nude appio -mutely equal lo the cu>nc*.ιiιi idυu >»i o yseii in an he "r.μ ot mc rπi tii'j ga ;nu o _,
Figure imgf000012_0001
-.υ a i -ate ol dl ge oi υ ygen c nceiiu fion may be periomied at least rvics, ana m y be perfoπned at least 3, 4, 5, 10, 15, 20, 30, 40 or 50 limes, or between 2 and 50 times, or between 3 and 0 or between 4 and 30 or between 5 and 20 or between 10 and 15 times, and may be performed 2, 3, , 5, 10, 15, 20, 25, 30, 40 or 50 times. Alternatively the measuring may be performed continuously over a period of time.
25 Optionally the step of measuring gaseous oxygen concentration may be repeated one or more times prior to cessation of the altering of step (i).
The IOR(s) is/are are function of oxidisable material in the pile which causes the change in the gaseous oxygen concentration. The IOR(s) is/are determined at the location(s) where steps (ii) and (iii) are carried out in the pile. The IOR So((θo, &s, T) is 30 frequently described by the Monod formula:
Figure imgf000013_0001
Here Smax is the maximum value of the IOR at atmosphere oxygen concentration; σι=<72=-0.05 are empirical constants; ωo and >s are the oxygen and sulfur mass fractions respectively at a given instant of time and at a given position in the pile of material; Ωo is an initial value of the oxygen mass fraction in the gas phase, which equals the oxygen mass fraction in the atmosphere and has an approximate value of 0.231 in the case that atmospheric air is used to alter the oxygen concentration within the pile; and Ωs is the initial mass fraction of sulfur. The factor A (T) is a smooth function of temperature equalling unity at relatively low temperatures, T< 40°C. Examples of piles of oxidisable materials include biooxidation piles, bioleach piles, waste rock dumps and the like. Whereas the present invention is intended primarily for use in the mining industry, it may also be used in other industries, for example food and agriculture, or other industries m which piles of oxidisable materials occur
The gaseous 0"» ygen coitcentiation may be expressed as any one of the following a pεiccnt ige bs- d on weight a percentage ba. e on volume mole fnelion mass fraction. "veigln fraction /olume b ictton in diι/ «>ιhu connnυnl u cd me.oι to e i '* "itch *■ i nn euirilion on ?enι?nri*><* she g « " ou_, o ^en eonecnιr * -n m y e e i.uic n iij ι p obe oi f μh"t sh)_ o j »ob .-. * l u> lι ιtι _ h ιnr ,π .d int ιlι . piL l m iic ul
The rate of change in gaseous oxygen concentration may be conveniently be determined by any one of the following means:
(i) subtracting one value of gaseous oxygen concentration from another value of gaseous oxygen concentration and dividing the result by the time difference between the measurement of the two values;
(ii) determining a slope of a line through some or all of the points representing the measured values of gaseous oxygen concentration on a graph of oxygen concentration against time;
(iii) determining a slope of a tangent to a curve representing the measured values of gaseous oxygen concentration on a graph of oxygen concentration against time; (iv) any other convenient means to determine the rate of change of gaseous oxygen concentration.
An equation may be used to calculate the IOR in the region adjacent to the probe. The following equation may be used to calculate an approximate value of the IOR of oxidisable material in the pile:
_ εp ϋil-a,)da>,
Figure imgf000014_0001
wherein:
So is an approximate value of the IOR;
ε is the volume fraction of the gas phase in the pile of oxidisable material; and '"(0) is the intrinsic gas density of the gas at the location in the pile at which the
IOR is detemiined, immediately after the altering of the gaseous oxygen concentration therein.
Equation 2 may be derived from mass balance equations for the total gas phase (Equation 3a) .md for the o"ygen density Equation 3b):
i »_ T (3a )
Figure imgf000014_0002
Figure imgf000014_0003
where: vg is an intrinsic pore gas velocity; and pg is a pore gas bulk density; and Do is the effective diffusion coefficient of oxygen in the porous medium; by assuming that diffusion of oxygen within the pile is insignificant. This assumption may be valid in the period shortly after the gas in the at least part of the pile has been altered.
In an example of the method, which is applicable to biooxidation and bioleach piles, the rate of change of oxygen concentration, and optionally also the IOR, is measured a plurality of times. The change with time in one or both of the IOR and the rate of change of oxygen concentration may be used to estimate one or more of:
(a) the change in the rate of conversion of metal substances in the pile to metal substances from which the metal is recoverable, as a function of time,
5 (b) the change in the rate of production of pollutants in the pile as a function of time, and
(c) the effective lifetime of the pile.
The measurements may be made sufficiently frequently and at sufficient time intervals to allow the estimates of (a), (b) and/or (c) to be made, but preferably not so frequently as to interfere unduly with the operation of the pile. The time interval between lo measurements may be for example between about 4 and 40 days, or between 5 and 35 days or between 6 and 30 days or between 7 and 25 days or between 8 and 20 days or between 10 and 15 days, and maybe about 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35 or 40 days The effeeli 'e lifetime of a pile may commonly be about 6 months for a bi " idation pile. Thus measurements may be made between 2 md 40 times or between is 3 and 35 or between 4 and 30 or between 5 and 25 or between 5 and 20 times, and may be made about 2, 3 4, 5 o, 7, l. c» 10 lc> 20 25 3d, 35 m -10 time- An estimate of the l l line or ^ be achtt »>'..< 1 by ;- rr pohling n; or more oi the 10T a the rate ol change oi o _, ecu toj icc t π r nto , and
Figure imgf000015_0001
ti υiπ i , iimc dπch > p rnctil r p.n ,M , j . H I die nun 1 ii in 4s ill h . en u loi , 1 ( lor e iip ""' < "» i , ' » ι i i ) lange (for e. ample 85-95% or 90-100%).
(i) The invention also provides a method of determining a spatial distribution of rates of change in gaseous oxygen concentration within a pile of material. Insertion of a plurality of probes into the pile may be accomplished by either locating the probes during building of the pile of material, or inserting probes into holes cut in the pile. The plurality 25 of probes may be arranged in a predetermined array. The distribution of probes is commonly dictated by convenience and cost. hi the case that probes are inserted into holes drilled into the pile, there may be a plurality of probes inserted into each of the holes at different depths in order to provide information about the spatial distribution of conditions within the pile. There may be a 30 plurality of such holes, each of which would commonly be no closer than 0.5 metre to another such hole. Preferably, for example, in a pile of 100 metres by 100 metres there may be about 9801 such holes, representing about 1 hole every 1 metre, or there may be about 361 such holes, representing about 1 hole every 5 metres, or there may be about 16 holes, representing about 1 hole every 20 metres or there may be a different number of holes (which may be between 9801 and 16 or greater than 9801 or less than 16). This 5 would commonly be the case when the pile was a mineral waste dump pile.
In the case that probes are inserted into the pile during construction of the pile, which is most commonly the case when the pile is a biooxidation or bioleach pile, the probes may be inserted into the pile in connected groups ("strings") which may be inserted at an angle to the vertical, the angle being dictated by convenience in the lo construction of the pile. Preferably a plurality of the strings is inserted into a pile, each of which would commonly be no closer than 0.5 metre to another such string. Preferably, for example, in a pile of 100 metres by 100 metres there may be about 9801 such strings, representing about 1 string every 1 metre, or there maybe about 361 such strings, lepiesenting about 1 string e 'ery 5 metres or there may be about 16 dungs lepresenting is about 1 siting every 20 metres or theie may be a different nunibei of stnngs (which may be between QG01 and 16 or greaier than 9801 or less than 16)
It will be undei dυo (hat the ile mav be construct. H in different "t ge-. Thus nun-all^ i fit t par! of die pile may be conrτπictsd * s nh ' iirci -y of tung, being w . I i the fu si p."M oi the ptS t eoiijirπuc , Vb"cqn )ib' ec «nd |HΠ oi ibr il m,ι be
-- ! con-iruuui . nh a seeoisπ _,,\ n| it ings being m.u' ii ι. the -.-.c ini μ-ni ot ie pile is constructed. The second part of the pile may be on top of the first part, or it may be beside the first part or it may be in some other location relative to the first part. It will be further understood that the pile may have more than two parts, and may have for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more than 10 parts, each of which may be constructed with a
25 separate set of strings being inserted as it is constructed, and each being, independently, on top of, beside, or in some other location relative to, any other stage of the pile.
The probe, or, in the event that a plurality of probes is used, at least one of the probes, may be capable of measuring the concentration of oxygen in the gas phase in the region adjacent to the probe. Advantageously, the probe(s) may also be capable of 30 measuring the temperature of the pile of material in the region surrounding the probe. More advantageously, the probe(s) may also be capable of measuring one or more other parameters of interest in managing the pile of material, for example gas permeability and gas pressure. Alternatively, separate probes may be provided to determine temperature and/or the one or more other parameters. Preferably the probe capable of measuring temperature is a thermocouple or a thermistor. The probe for measuring another parameter of interest may be a manometer. The period of time over which the measurements are made may be any period from about 1 hour to several days (eg 1 to 5 days or 1 to 3 days or 1 day) or even weeks. The time period is preferably less than about 15 hours or less than 12 hours or less than 10 hours. The time period may be in the range of 1 to 15 hours, 1 to 14 hours, 1 to 13 hours, 1 to 12 hours or 1 to 10 hours. The time period may be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 hours. More preferably, the measurements are made over a period in the range of from about 1 to about 5 hours. In the case of bioleach and biooxidation piles, this may help to ensure that the determination of the IOR causes as little as possible disruption to the operation of the piles, and may enable calculation of the IOR to be made sufficiently rapidly so as to permit effective control of the operational conditions of the pile of material hi lhe case of waste mineral dump piles, this may enable rapid classification of the dumps based on the measured IOP or distribution of the IORs.
Prefct bly, the measurement of oxygen concentration in the region adjacent to the probe and the subsequent cnlcul ition of the lύ( ' do not imeileie signifϊcnnih, >«iih the o in ji im i i t he pile υf nt nei i f The method may include a step in which the calculated IOP. is used to make decisions concerning operation of the pile. Optionally, data relating lo other parameters of the pile, for example temperature, are also used in making said decisions. Preferably, in the case that the pile is a biooxidation or a bioleach pile, the decisions relate to adjusting the operating conditions of the pile of material. More preferably the decisions relate to improving the operating conditions of the pile of material.
When IOR, or the spatial distribution thereof, is used in a method for controlling the operating conditions of a pile of material, other parameters may be measured in order to determine how to adjust the operating conditions of the pile. Commonly, one of the other parameters is temperature. The step of adjusting may include aerating the pile and/or contacting the pile of material with water or aqueous liquid. The pile may be aerated and/or contacted with water or an aqueous liquid at a rate sufficient to improve the oxidation rate of the pile of material. The step of adjusting may also include using other methods to affect the oxidation rate of the pile of material. Preferably aerating and/or contacting with water or aqueous containing liquid are at a rate sufficient to optimise the oxidation rate of the pile of material. The oxidation rate may be a rate of biooxidation of sulfur-containing materials in the pile.
5 Alternatively or additionally, the calculated IOR or a distribution thereof, optionally together with other data gathered from the same or a different probe(s), may be used for computer modelling or simulation of the operation of the pile of material, in order to determine the effect of specific conditions on the operation of the pile of material.
In an example, the method includes the step of aerating the pile of material and lo then ceasing the aeration before the measurement of oxygen concentration is made or before the first of two or more measurements of oxygen concentration is made, in order to provide a gaseous oxygen concentration in the pile of material that is approximately homogeneous and is higher than the gaseous oxygen concentration before the aerating. Alternatively, the oxygen concent ration within the pile may be altered using
Figure imgf000018_0001
or a is mixture oi gases, said mi '.tine containing oxygen. The oxygen concentration in the mb ture of gases is greater than the oxygen concentration in the gas in the pile prior to the altering ai the location^ ) where the measurements are made. X hi mtageously. lite sieps of aer 'tin*, the pile m dlering rh= o , yen coucentr stion • qihm ihe pile and determining ill. l r in i d >c i s c 'I C I t u i lb m ur * MM id i mi -igeuujy (b*, )nh iu < i n y be _ ι ι .- e lte n uont mo»ing the piobef " )
In another example, the or each probe is inserted into a cavity in the pile of material that has been aerated such that the oxygen content of the gas phase in the cavity and in the surrounding region is substantially the same as the oxygen concentration in the ambient atmosphere outside the pile of material. The region preferably has a radius of greater than
25 3 metres, more preferably greater than 4 metres and still more preferably greater than 5 metres. This embodiment may provide an initial level of oxygen in the region surrounding the probe that is similar to the level in the atmosphere outside the pile of material. Alternatively, the oxygen concentration in the cavity and the region surrounding the cavity may be altered before the measurement of oxygen concentration, using oxygen or a
30 mixture of gases, said mixture containing oxygen. Preferably, the cavity into which the probe is inserted is formed using a drill that passes air, oxygen or a mixture of gases, said mixture containing oxygen, into the cavity as the drilling progresses. The cavity may be a hole that has been drilled in the pile. The cavity or hole may be sealed or closed after the probe(s) is (are) appropriately located therein. The sealing or closing is conveniently achieved by backfilling the cavity or hole.
Preferably the time elapsed after aeration of the pile of material and the distance of the probe from the surface of the pile of material are such that the diffusion of oxygen from the outside of the pile of material to the probe is not significant. This may serve to ensure that equation (2) provides an acceptable estimate of the actual IOR, by satisfying the assumption that diffusion of oxygen from outside the pile into interstitial voids is insignificant. The condition for ensuring that this assumption is satisfied is given by:
Figure imgf000019_0001
where:
/ is the distance of the probe from the surface of the pile;
Do is the effective diffusion coefficient of oxygen in the gas within the pile; and
1 is the time after aeration has ceased. The method iccording lo due first embodiment of the present invention offers the
;a v,mj --ζc ih <ι pile o -id ι|ic>n μerfomum e «. m be determined on m ongoing -, κ '"lfhuiu ft • ϊii to i u t tern ii indicaiυiL ι"hι ι *ho » ι <-ιgm fn .un tun
Figure imgf000019_0002
lxlnud ic iH'iI j »i |ι i i too n nice
When IOR or a spatial distribution thereof is used in a method for constructing, and controlling the operating conditions of, a pile of material, a computer model may be used to determine at least one parameter of construction of the pile. The model may be based on a deterministic formulation of multiphase flow through porous media, for example a computer model as described in Australian Patent No. 6083790, the contents of which are incorporated herein by reference, or a computer model similar to that model. Commonly, Alternatively or additionally, the calculated IOR, optionally together with other data gathered from the same or a different probe(s), may be used for computer modelling or simulation of the operation of the pile of material, in order to determine the effect of specific conditions on the operation of the pile of material. The computer modelling may use the same model as that described above or it may use a different model. In a system for determining a rate of change in a gaseous oxygen concentration within of a pile of material, according to the present invention, the means for measuring the gaseous oxygen concentration may comprise a tube through which a sample of the gas to be measured is conveyed to a sensor capable of measuring oxygen concentration. When a plurality of the probes are used, each tube may be connected to a separate oxygen sensor, or one or more of the oxygen sensors may be connected to a plurality of tubes. There may additionally be means to control from where in the pile the sample of gas was taken. The means to control may comprise a plurality of valves linked to a means to control the valves, for example a computer. There may optionally be one or more filters, either at the end of the tube(s), at some location within the tube(s) or near the oxygen sensor(s), the filters being capable of removing materials detrimental to the performance of the oxygen probe or sensor, for example particulate material, dust, CO and moisture. In a system for determining a spatial distribution of rates of change in gaseous oxygen concentration within a pile of material, the plurality of prob s may be arranged within the pile in a predetermined array.
If more than one probe is connected lo a particular sensor then there may additionally be means to -eleJivdy ditccl gat fiom one piobc to the sensor it tv p-nlicnlji time The r wyeiu ma > include, meaii-"* tor n ine. i 1*- .a one »d the c dud 'fed I f _, tht ' i _ ic ii c uie ih . don nd die l i tiprr irnre m m il ; eu mr * nc . r nnic _«pe' mi ni lh _* pile I he ni . m lo m il dι.ι i ι« >ι, π ι ι c mtipH t iii . m to <ι |pι 1 the operating conditions of the pile of material.
In a particular aspect of the invention, there is provided a system for controlling the operation of a pile of material, comprising:
(i) one or more probes capable of being located within the pile of material; (ii) means for altering the gaseous oxygen concentration in at least a part of a pile of material and means for stopping the altering;
(iii) means to determine (a) rate(s) of oxidation of material within the pile;
(iv) means to determine the IOR or a spatial distribution of the IOR within the pile; (v) means to determine temperature and optionally a spatial distribution of temperature within the pile; (vi) means for controlling the provision of the one or more materials to the pile.
The system may include means for coupling the probes of (i) to the means to determine of (iii) and (v). The one or more materials in (vi) may be air or other gas, water or other aqueous liquid, for example. The means of (iii), (iv) and (v) may include a computer. The means of (vi) may be a computer linked to means for providing air or other gas to the pile and/or means for contacting one or more portions of the pile of material with water or aqueous liquid.
The probe(s) maybe capable of measuring gaseous oxygen concentration, and optionally they may also be capable of measuring temperature, and optionally also other parameters of relevance to the operation of the pile of material. Alternatively, separate probes for measuring gaseous oxygen concentration, temperature and optionally the other parameters may be located close to each other in a group. There may be between 2 and 70 or more of the probes or groups of probes within the pile. The numbei of probes will depend on the she of the pile and the chosen distance between piobes. In particular there may be between 2 and 50 or more of the probes or groups of probes within the pile. More particularly there may be between 2 m>) 30 or more of the probes or groups ol probes •Mihm the pile fwen tπoi p irtic tii rl ' ihei c iu be b.t 's )i 2 iπd 20 or niur*" ol the pi b.- i oii *- oi i ol 1 «'iιϊιιtι t e pi le ' nil I I IM C p. πι» id ,ι I > i lici t* y be hei - - e = n . atid l i niof . « <t ' u i i ' e oi j ' - -ι probe lilnn die pile Pi ci.t.-bly any n location within the pile at which oxygen concentration is measured will be between 0.5 and 10 metres or more from any other such location. More preferably any two such locations will be between 0.5 and 7.5 metres apart, still more preferably between 0.5 and 5 metres apart, even more preferably between 1 and 4 metres apart, even more preferably between 1 and 3 metres apart and still more preferably between 1 and 2 metres apart.
The means for providing air or other gas to the pile may be capable of providing the air or other gas selectively to different portions of the pile at different rates. Similarly the means for providing water or other aqueous liquid to the pile may be capable of providing the water or other aqueous liquid to different portions of the pile at different rates. The system may also include means for adjusting other parameters of relevance to the operation of the pile in response to the determined IOR or spatial distribution of the IOR in the pile. The means for determining the IOR or a spatial distribution of the IOR may be a computer. The means for controlling the provision of air or other gas and of water or other aqueous liquid to the pile may comprise a series of valves connected to the computer. The means for controlling the provision of air or other gas and/or water or other aqueous liquid to the pile may comprise means to control the provision of the air or other gas and the water or other aqueous liquid selectively to different portions of the pile at different rates.
Similar mathematics to that shown above has been derived for piles of sulfidic materials by Bennett and Ritchie (Hydrometallurgy, 72 (2004), 51-57). The oxygen concentration, u (x , y , t), in the gas phase in the pore space of a heap of sulfidic material may be calculated using:
— ^— + div[u*εgvg -D0Vu*] = -βg Ss(ω ,ω ;;,T) (5) where
D0 = the oxygen diffusion coefficient;
SJ(ω § . ω l,T) = the intrinsic oxidation rate of the sulfidic material; T -= the temperature at the point (-_ ,y ); β„ -. the ratio of I he mass of ox^een used lo the mass oi sulfur consumed in sυlfide
O ii tion: — .i huriiυninl .τι.
Figure imgf000022_0001
t he nπui-lon ol ihe h . 'p in t he the n o i -oiili I dire lion ι_, I n '-. i ni ai - d lo m*- x,y dimensions. The mass fraction of oxygen, ωf , in the gas phase and the mass fraction, S S , of sulfide sulfur in the solid phase are also functions of x , y and t. Using the dimensionless variables: x=x7x0, y=y7h, S=Ss/s„ and u=u /u0; where
X0 = the width of the heap (m); h = the height of the heap (m); u0 = the oxygen concentration in air (kg m"3); and SQ = the maximum value of the intrinsic oxidation rate (kg (O2) m"3 s"1)
Equation 5 may thus be written as: 1 β β g_„sSi-Os
-S(ω§,ω s,T) . (6)
Figure imgf000022_0002
Examination of Equation 6 shows that, in order to achieve a high oxidation rate at all points in a pile of sulfidic material, the second term in the square brackets must be much smaller than the first. Thus the specific gas discharge rate, εgvg, should be much greater than D0/h. For a typical pile the latter term is commonly about 5 x 10"7 m/s. This value of specific discharge rate is readily achievable in practice. It can be shown that for the oxidation rate throughout the heap to be near the maximum value, the specific discharge rate should be about 10"4 m/s. The gas discharge rate should be high enough for the second term in Equation 6 to balance the third term. Such discharge rates can be achieved by providing air to the base of the pile. The pressures required are quite modest
1 1
(between about 100 and 10,000 Pa) for a gas permeability of greater than about 10" m . When the supply of air is switched off, the gas specific discharge rate decreases sharply, hi most large waste rock piles, gas transport is dominated by diffusion at locations sufficiently far from the sides of the pile This is likely lo be the case for mosl bioo idation and bioleach heaps as well W hen aeration is ce ed, the first term in the square brad ets oi Equation o can be neglected, and Equation 6 becomes,
Figure imgf000023_0001
. 111.. H i Hl'~M pi le 111. tdili t u mJl_ niiich gi e Oei th m the her hi th-, cend • . i iti ii i di " "'jini . 1 i »ι l et uι t». U . ion " ' in [»e n _l-. ι - f _ ρ ι< I Jn_ u .i i he o _ j rll dlt lu i n cυctt ici . in in be bom 5 10 in *-" md 1 U in i' u th . h . tghi "I i h e pile T hu the multiplier outside the square brackets may commonly be about 5 ^ 10" ε . To ensure that a large fraction of sulfide sulfur is oxidised in a biooxidation heap in a typical time of about 6 months, the intrinsic ooxxiiddsation rate should be high, for example about 5 x 10" kg
Pgi*-*o
(O2) m" s" . The multiplier will then about 7 10"4 s"1. Thus the IOR dominates uc the behaviour of the oxygen concentration in the pore gas over time as the system relaxes from the pseudo steady state after aeration has been stopped. Consequently, measurement of the rate of decrease of the oxygen concentration at a point in the heap provides a measure of the IOR of the sulfidic material at that point. Measurement of the rate of change of the oxygen concentration at a variety of locations throughout the heap provides a distribution of sulfide sulfur oxidation rates through the heap, since the stoichiometry of the sulfide oxidation reactions is known. Waste rock dumps are typically much higher than bioheaps, commonly being up to 25m or more, but the oxidation rate of the sulfidic material is typically much lower, commonly about lx 10"8 kg (O2) m"3 s"1. The multiplier at about 7x10 is still greater than
Figure imgf000024_0001
(D0/h2) at 8x10"9. Thus it is still probable that immediately after cessation of drilling the time dependence of the oxygen concentration near the probe hole may described by a simple rate equation.
A preferred mode of carrying out the invention is described below with reference to Figures la, lb, 2a, 2b and 3. In this description, the numbers of the following: probes, collections of probes, groups of probes, strings of probes, holes, outlets for water and air, and other components described; are shown by way of example only and should not be taken as in any way limiting the in ention. hi the case of a waste rock pile, illustrated diagrammafically in Figure l holes 102.104 aid 106 are drilled 'ertically (or alternatively they may be drilled it some different angle) into a pile of waste rock 101. A typical aste rod pile may be between lot) and 1000 metres vi and between lo aid 1 0 metres oi more high. The drilling l hole- lino i. pile t_ JTJWΠ eπtiter detail in Fi-n rr 2 Coile< H-.I ot pmh 112, 11 --I ml lloiF "no.1 ι) coiupi" πt_r po-be cap bl. t d* .--aiiituHi'j g np- «> *. c in cull M, »H tion ill ' lit^. diet ith l.tilp.t Hi', ni'/in oth.i p lLι»,n_!- ι o li Mi ni the operation of the pile, are located into holes 102, 104 and 106. Collections of probes 112, 114 and 116 comprise groups of probes at different depths within the holes 102, 104 and 106. This is shown in greater detail in Figure 3. The probes of collections 112, 114 and 116 are located sufficiently far from the surface of the pile thai diffusion of oxygen from outside the pile is negligible during the period of a measurement. Although this depends on a number of factors (Equation 4) a typical minimum distance to the surface of the pile may be about 0.5 to 1 metre. Collections of probes 112, 114 and 116 (which include collections of tubes 152, 154 and 156) send electrical data to computer 140 by means of collections of electrical cables 122, 124 and 126 and send gas samples to oxygen detectors 142, 144 and 146 by means of collections of tubes (probes) 152, 154 and 156. It should be noted that certain types of probe, for example thermistors, require a device such as a signal transducer, to convert a signal from the probe to a signal suitable as input for a computer. It will be understood that such devices, although not shown in the Figures, are in fact present when necessary. Oxygen detectors 142, 144 and 146 are also connected to collections of electrical cables 122, 124 and 126 and transmit data through them to computer 140. Alternatively, signals maybe sent from collections of probes 112, 114 and 116 and oxygen sensors 142, 144 and 146 to the computer 140 by means of
5 transmitters or other convenient method. Optionally there may be more than three or less than three oxygen detectors connected to collections of oxygen tubes 152, 154 and 156. For example, there may be 1, 2, 4 , 5 or 6 or more oxygen detectors. During the drilling of holes 102, 104 and 106, air is provided to the holes as shown in Figure 2 (for a typical hole 215). This creates a zone of aeration 235 in which the oxygen concentration is o approximately the same as in the outside atmosphere. As soon as is convenient after insertion of probes into holes 102, 104 and 106, the holes are sealed by backfilling with backfills 132, 134 and 136, and data acquisition from collections of probes 112, 114 and 116 is commenced. The data acquired over a period of approximately 10 to 12 hours is sent to the computer 140 which then determines a rateof change in o"* ygen concentration for each o" ygen probe. Fiom that and Irom othei data the computer 140 can then determine a spatial distribution of the IOP and optionally also of other paiarnelers Alternatively- ι w data may be stored in the compiler for subsequent offline nnalysr Tlnr dfcniafiv*; in i be commonly t &l in the
Figure imgf000025_0001
of »<-. - ie ιucl ρtler
Dui Jii i . n iryei ' -u >i In «> ft <πon/l«ιo)e n.h pile dln-ai a _ i dι ι >ι aπni tie dl_ ■ I-* ' '.H i e l b H pi 11. - 2 l Z ' t id ' i _ ■ b m hi 11 n M h i l it m i m u r I ' iinlf.i di e initially laid on the ..lie. The pipes are fitted with air ilov/ contiol 'ab e 252, 254 and 256, which are connected to computer 220 by cables 262, 264 and 266. Alternatively, signals may be sent from the computer 220 to the valves 252, 254 and 256 by means of a transmitter or other convenient method. Rock is then laid on top of pipes 242, 244 and 5 246 to form pile 201. Strings of probes 202 (including tubes 223, 225, 227), 204 (including tubes 229, 231 and 233) and 206 (including tubes 235, 237 and 239) are located in pile 201 as it is being constructed. Strings of probes 202, 204 and 206 contain individual groups of probes 222 (including tube 223), 224 (including tube 225), 226 (including tube 227), 228 (including tube 229), 230 (including tube 231), 232 (including 0 tube 233), 234 (including tube 235), 236 (including tube 237) and 238 (including tube 239). Each of these groups of probes contain individual probes which are capable of measuring gaseous oxygen concentration, and optionally temperature and/or other parameters relevant to the operation of the pile. The strings of probes in Figure lb are each similar to the collection of probes shown diagrammatically in Figure 3, although they are located at an angle in the pile, and are located in the material of pile 201 rather than being located in a backfilled hole. The groups of probes 222, 224, 226, 228, 230, 232, 234, 236 and 238 are located sufficiently far from the surface of the pile that diffusion of oxygen from outside the pile is negligible during the period of the measurement. Although this depends on a number of factors (Equation 4) a typical minimum distance to the surface of the pile may be about 0.5 to 1 metre. Probes 223, 225, 227, 229, 231, 233, 235, 237 and 239 within groups 222, 224, 226, 228, 230, 232, 234, 236 and 238 respectively are designed to measure oxygen concentration and comprise a tube for conveying air samples to oxygen detectors 247, 248 and 249. Alternatively, there may be more than three or less than three oxygen detectors connected to collections of oxygen tubes 223, 225, 227, 229, 231, 233, 235, 237 and 239. For example, there maybe 1, 2, 4 , 5 or 6 or more oxygen detectors. The oxygen detectors are located externally to pile 201. This is shown in greater detail in Figure 3. Groups of electrical cables 212, 214 and 216 transmit data from probes 202, 204 and 206 and from detectors 247, 248 and 24--* to computer 220. Alternatively, dal may be sent to the computer 220 by means of a tiansmitier or other convenient method, stater pipes 272, 274 and 276 are located on oi abo .c ihe top of pil 01. h lch *n pipe-* 272 274 md 176 may ha . e one or oie outlet "■ IOL ■-/ i .i ( l i ilij j t tl ' ii r ιbι oiih pin.. 272 2?J id 27? > tn » ' hi conuol led b* •* i -^ 2. 2 2 .-' nun 2<~ d'icϊi in .' ti me' le ιo .ompiii π 22θ b ' decu ie l c bl - "-M - 2M- -no 2" *0 l.ei π.'ii w ely, . I'll 1. Hi » b. ' :uι n oiji i he coinpniei 2.0 io 1 . . 2 - 2 ".-'-! ul ' 2 • » by means of a transmitter or other convenient method. The watei supplied to pipes 272, 274 and 276 may have various materials, for example acid, ferric ions and/or other ionic species or other chemicals dissolved in it for the purpose of improving the operation of the pile.
Prior to determining the IOR or a spatial distribution of the IORs, air is passed through pipes 242, 244 and 246 in order to provide oxygen to the parts of the pile in which probes 223, 225, 227, 229, 231, 233, 235, 237 and 239 are located, such that the oxygen concentrations at those locations are approximately the same as the oxygen concentration in the atmosphere outside the pile. The air flow through pipes 242, 244 and 246 is then stopped by closing valves 252, 254 and 256. These valves remain closed throughout the period in which data is acquired for determining the IOR or a spatial distribution of the IORs. Alternatively, air flow may be controlled by turning on or off blowers, fans or other means for providing the air to pipes 242, 244 and 246. Either before the stopping air flow or immediately after it, a measurement of oxygen concentration is made by each of the probes in the pile, using detectors 247, 248 and 249 to measure the oxygen concentration of samples of gas taken by probes 223, 225, 227, 229, 231, 233, 235, 237 and 239. At the same time, measurements of temperature and any other desired parameters are made by detectors in strings of probes 202, 203 and 204. The data so acquired is sent to the computer 220 by means of groups of cables 212, 214 and 216. Measurements of oxygen concentration, temperature and optionally other parameters are then made at a number of times over a period of approximately 10 hours. Data from these measurements are transmitted to the computer 220. The computer then processes that data to determine the IOR or a spatial distribution of the IORs, and optionally also other operating conditions of pile 201 or spatial distributions of the other conditions. It may then determine what changes need to be made to the operating conditions of pile 201 to improve its operation. The computer may then send signals to valves 252, 254, 256, 282, 284 and 286, and optionally to other devices capable of influencing the operating conditions of all or part of pile 201„ in such a way as to impro /e the opera ling conditions in al! or part of the pile 201.
With reference to Figure le, pile 405 compiises first part 407. with strings 410, 412 md -1 14 and s con pan 40", « th siring* 4 i d 41.J and 420. Λir pipe: 430 432 aid 434 ic lθι t en brio « nι i p n 4 5 τ« <r >tin _r Hi ι p in 405 md n piμe 4 " o 43 md 440 ) ιc !• i. r-.d b. lo ' ihe ci a i, π -|T ioi ι.ι mn . >_ .olio u iu7 he . H μip.-. u e ύ ten i Ii ii Ho ' eoπitui ' I : 450 45 md 45-1 aid an ilo ,' cunπ υi > A es -*."o - X and 460 respectively. These valves are connected to computer 470 by cables 80, 4£2, and 484, and 486, 488 and 490 respectively. The individual probes in strings 410, 412 and 414 are connected lo oxygen detector 415 by a collection of tubes 422, and the individual probes in strings 416, 418 and 420 are connected to oxygen detector 425 by a collection of tubes 427. Oxygen detectors 415 and 425 are connected to computer 70 by cables 490 and 492 respectively.
In constructing pile 405 air pipes 430, 432 and 434, fitted with valves 450, 452 and 454 and cables 480, 482, and 484 are initially laid on the site of the pile. As the material of first part 407 is deposited on the site, strings 410, 412 and 414, connected to computer 470 by collection of cables 422, are incorporated in pile 405. In a subsequent construction step, air pipes 436, 438 and 440, fitted with valves 456, 458 and 460 and cables 486, 488 and 490 are laid on or in the top of first part 407. As the material of second part 409 is deposited on top of first part 407, strings 416, 418 and 420, connected to computer 470 by collection of cables 427, are incorporated in second part 409. Once pile 405 has been constructed, IOR of the pile, or a distribution of IORs, may be determined in a manner similar to that described for Fig. lb. IOR, or a distribution of IORs, may determined separately for first part 407 and for second part 409, or it may be determined for pile 405 as a whole. In order to determine a distribution of IORs for pile 405 as a whole, the pile is initially aerated through air pipes 430, 432, 434, 436, 438 and 440, by opening valves 450, 452, 454, 456, 458 and 460, under control from computer 470 via cables 480, 482, 484,486, 488 and 490, and subsequently the valves are closed to stop the aeration. Either before the stopping air flow or immediately after it, a measurement of oxygen concentration is made by each of the probes strings 410, 412, 414, 416, 418 and 420, using detectors 415 and 425 in to measure the oxygen concentration. The data so acquired is sent to computer 470 by means of cables 490 and 492 Measurements of c ygen concentration, temperature and optionally other parameters are then made al a number of limes over a period of appro imately 10 hours. Data from these measurement-, are transmitted to the computer 470. The computer then processes that data to determine a spatial distribution oi the IOP -,
Hj'jure 2 ho * ■ dl id until me repl escalati n of a >. i n 215 founed in ιh; oi uc in . l eu ιl ol pile _o5 C nil bit 22 " inch m ι l ." imp) , b. n n ι p icHr' ton m f ij I ■ l u l l bl I U .il l i i KI I H l i_ 21 ~ H id In d> I I I-. • Upj U . . Hi H i" " i ll ' •_ > \ >_ I air may move tlnυugli ihe porous material ol pile 205a as shown by ie an j in Figure 2, such that the aerated region 235a has an oxygen concentration approximately equal to that of ambient air. The radius of aeration is represented by the radial distance from the hole to the boundary of the aerated region. In order to provide sufficient lime over the length of a 10 hour measurement of the IOR, the radius of aeration should be preferably at least 5 metres.
Figure 3 shows a diagrammatic representation of one of the holes 102, 104 and 106 of Figure la, containing probes and backfill 340. As noted previously, this shares many features in common with the strings of probes 202, 204 and 206 of Figure lb. In Figure 3, a plurality of probes is inserted into hole 350, which is located in pile 301. The probes are organised in groups of probes 352 and 354 which are located at different depths within hole 350. Each of groups 352 and 354 comprise probes for measuring gaseous oxygen concentration (302 and 304), temperature (306 and 308) and another relevant parameter (310 and 312). Probes 306, 308, 310 and 312 are connected to computer 320 by electrical cables 326, 328, 330 and 332. Alternatively, signals may be sent to the computer 320 by means of a transmitter or other convenient method. Oxygen concentration probes 302 and 304 comprise tubes 322 and 324 which can transmit samples of gas from the vicinity of groups 352 and 354 to an oxygen detector 318, which is conveniently located outside the pile. Oxygen detector 318 comprises pumps 314 and 316, which pump gas samples from tubes 322 and 324 to the oxygen sensor 319 located within detector 318. Valves 315 and 317 (controlled by computer 320 using a means not shown here for reasons of simplicity) select which of the probes is in service at a particular time. Signals from oxygen sensor 318 are transmitted to computer 320 using electrical cable 323, or using a transmitter or similar convenient means. Temperature probes 306 and 308 are preferably thermistors or thermocouples.
Figure 4a shows the dependency of oxygen concentration upon time within a biooxidation/bioleach pile for two different examples of the operational conditions of the pile (pile 1 and pile 2) as obtained from numerical modelling. Figure 5a shows the dependency on time of rhc relative deviation r of (he approximate value of the JOP- from iis tnoi e previse τ lue >'> ' te cπfaed fro E uaa on 1 );
} -' t '. l
The estimated value of the IOP,, obtained using Equation 2, agrees well with the more precise value from Equation 1 if the measurements of oxygen concentration are conducted within several hours of cessation of aeration of the pile and within the bulk of the pile. Typically for a biooxidation/bioleach pile, measurements would commence immediately following the cessation of aeration, or alternatively one or more measurements may be made before the cessation. The condition for determining the minimum distance of probes from the surface of the pile is given by Equation 4. These conditions serve to ensure that diffusion of oxygen from outside the pile is minimal during the period of the measurement. Curves 5, 9, 11, 10 and 1 in Figure 4a correspond to locations which are close to the pile surface, and consequently which violate the conditions described above. The other curves, 2-4 and 6-8, correspond to locations within the bulk of the pile. The time period within which reliable measurements may be obtained depends on the location of probes from which the measurements are taken. Consequently in Figure 4a, the locations within the pile corresponding to curves 5, 9, 11, 10 and 1 have oxygen concentrations that are higher than would be expected from Equation 2, since the oxygen at those locations has been augmented by oxygen diffusing from outside the pile. Figure 5 a shows that the deviation of the calculated IOR from exact value of the IOR increases with time, as the greater time periods allow more oxygen to diffuse from outside the pile to the location(s) of the probe(s). Curves 2-4 and 6-8 do not show these deviations from the theoretical values since the locations of the probes are sufficiently far from the surface of the pile that the amount of oxygen that can diffuse to those locations over the time of the test is insignificant. Figure 4b illustrates the dependency of oxygen concentration upon time as a function of depth and of size of the aerated region, as obtained from numerical modelling of a waste rock pile such as that shown diagrammatically in Figure la. Figure 5b shows the deviation of the calculated oxygen concentrations of Figure 4b from the more precise values obtained from Equation 1 hi Figure 4b and Figure 5b dal a is shown for 5 different depths within a 20 metre deep pile- curves 1 to 5 represent dat al distances of 1 0 5.5 10 o. 14 5 and 19.0 metres respectively from the base of the pile Three sets of such data aie sh wn' data repi ev nt d by d idiec de^uthc^ a h le »? itb n 2 meuc radii"; of the -.our
Ol lei il'on d H i t epi CCnted b_ d i h-dol i ioi i > i i iet i e 1" djii. nd olld llli .-' ϊ e tt. -Ill '"dn .f i . i d i n lπf iiι " 4 ' ι ho > ιh t MI. I ι _ . ι l b t ' _i"iι oi .-I " <« ». ( i he "i n Ik r i hi d . hit Hi " • ι ι co mi t on I tin i» u . m . i i i idiπ oi 'l l' »n lι>. » _ _■ <ι concentration diops substantially m only a ie -v hours, since there ι_ a hi ailei reservoir ot oxygen m the surrounding material. By contrast, for a 5 metre radius of aeration, the decline in oxygen concentration is much smaller and is approximately linear over time during the 10 hour period described. Correspondingly, the deviation of the approximate IOR from the more precise value of the IOR from Equation 1 is greater when the radius of aeration is smaller. For a radius of aeration of 5 metres (solid lines), the relative deviation is small and relatively constant. Figure 4b also shows that at a depth of only 1 metre from the surface (curve 5), the oxygen concentration is higher than for the other four deeper locations. This is due to augmentation of the oxygen due to diffusion from outside the pile. For small radii of aeration (2 and 3 metres), the relative deviation of the IOR at 1 metre depth, shown in Figure 5, is less than for the deeper locations, since the diffusion of oxygen from outside the pile partially offsets the depletion of oxygen due to the small size of the oxygen reservoir, hi the case of a 5 metre radius of aeration, location 5, near the surface, shows a slight positive relative deviation after some time, since the depletion is small due to a larger region of aeration, and diffusion from outside the pile more than compensates for it.
Figure 6 shows a graph of the normalised IOR as a function of normalised oxygen concentration as described by the Monod formula (Equation 1). This graph describes the behaviour of the IOR when the actual material being tested is the same. It shows that the IOR depends on oxygen concentration, so that when oxygen concentration is below the atmospheric level, the IOR will be lower than its maximum value. It further shows that the deviation of the IOR from its maximum value is relatively slight for higher values of oxygen concentration. For example, when oxygen concentration is only 50% of the atmospheric level, the IOR is over 90% of its maximum level. However at low levels of oxygen concentration, the change of the IOR in response to a relatively small change in oxygen concentration is much larger.

Claims

Claims:
1. A method of determining a rate of change in a gaseous oxygen concentration within a pile of material, said pile of material comprising both solid phase and gas phase, comprising the steps of: (i) altering the gaseous oxygen concentration in at least a part of the pile of material; (ii) measuring the gaseous oxygen concentration in at least one location within that part of the pile of material altered by said gas containing oxygen; (iii) repeating said measuring a sufficient number of times at said at least one location to enable detennination of a rate of change in the gaseous oxygen concentration, wherein the altering of step (i) is ceased at least prior to said repeating; and (iv) determining ihe rate of change in the gaseous σ* ygen concentration in said ai least o 5 location
2 Th method of claim 1 wherein said alteπng comprizes, passing a cont ainin o » gen thiongh c id m l ast a p m of
Figure imgf000032_0001
pile
. Tf r i u l'i « ' • ■ • 1 n i i 1 iurdi«- r < > u pi t πa t l r le p o l ri ei .i u nnπu iπ im n π ie o iii aiυti r ae (IOP ) n ..aid a Laα n Soc aton m lh_ pile
. The method of cl
Figure imgf000032_0002
is used to calculate an approximate value of the IOR of oxidisable material in the pile, wherein:
S0 is an approximate value of the IOR; ε is the volume fraction of the gas phase in the pile of oxidisable material; and p'"(0) is the intrinsic gas density of the gas at the location in the pile at which the IOR is determined, immediately after the altering of the gaseous oxygen concentration therein.
5. The method of claim 2 wherein the concentration of oxygen in the gas containing oxygen is sufficient to make the oxygen concentration in the at least one location approximately equal to the concentration of oxygen in air.
5 6. The method of claim 1 comprising the steps of aerating at least a part of the pile of material and of ceasing said aeration before the step of measuring the gaseous oxygen concentration.
7. The method of claim 1 wherein the step of measuring comprises the steps of : o (i) transferring a sample of gas from the region surrounding the probe to a location external to the pile; (ii) passing said sample of gas to a device capable of measuring gaseous oxygen concentration; and (iii) using said device to measure a gaseous oxygen concentration of said sample of gas.
C The method of claim 1 wherein the time at winch each of the steps of me loimn are- ρeι loπued ι = i <-, corded
< * I he me iliod ol . l am I di . m > h t .p o) lie- m . ' i ipi i ionnin ji ■
• π (y in Hi . f il l . H I uni . n -1 uc u i h n t he s j <j .n C ΉI . IU ol dι . j • p ι c . in _ π-t » Λ Π _ and in the surrounding region is substantially the same as the oxygen concentration in the ambient atmosphere outside the pile of material.
5 10. The method of claim 9 wherein a probe for measuring oxygen is inserted into the cavity.
11. The method of claim 1 wherein the rate of change of oxygen concentration is measured a plurality of times, and the change with time in at least one of the IOR and the 0 rate of change of oxygen concentration is used to estimate at least one of:
(i) a change in the rate of conversion of metal substances in the pile to metal substances from which the metal is recoverable, as a function of time, (ii) a change in the rate of production of pollutants in the pile as a function of time, and (iii) an effective lifetime of the pile.
12. A method of determining a spatial distribution of rates of change of gaseous oxygen concentration within a pile of material, said pile of material comprising both solid phase and gas phase, comprising the steps of:
(i) locating a plurality of probes in the pile;
(ii) altering the gaseous oxygen concentration surrounding at least two of said probes;
(iii) measuring an oxygen concentration in the gas surrounding the at least two of said probes in the pile; (iv) determining a rate of change in oxygen concentration of the gas surrounding the at least two of said probes in the pile wherein said delemnning comprises measuring the o-.ygen concentration in the gas
-unrounding it least two oi the probes after the altering of tep (ii) has been stopped and ( ' i determining a patial d lithuiϊon oi ιa1er o{ ch e in ate u- o ygen c n1 cnii lion in ιlι. pile
i ."• Tii _ ui.ltiod »ι I um 12 n .i ciii _ to di n ing cj n . p i m^ a i-. containing oxygen through the locations of the at least two of said probes
14. The method of claim 12 additionally compnsmg the step of determining a spatial distribution of IORs within the pile.
15. A method of controlling the operating conditions of a pile of material, said pile of material comprising both solid phase and gas phase, comprising:
(i) determining information selected from the group consisting of an IOR of oxidisable material in the pile and a spatial distribution of IORs of oxidisable material in the pile; and (ii) adjusting at least one operating condition of the pile.
16. The method of claim 15 wherein the step of adjusting comprises a process selected from the group consisting of aerating at least one portion of the pile and contacting at least one portion of the pile of material with a liquid selected from the group consisting of water and an aqueous liquid.
17. A method for constructing, and controlling the operating conditions of, a pile of material, said pile of material comprising both solid phase and gas phase, comprising:
(i) determining at least one property of the material;
(ii) using the at least one property in a model to determine a value of at least one parameter of construction of the pile of material;
(iii) constructing the pile using the value of said at least one parameter of construction; (iv) detennining information selected from the group consisting of an IOR of oxidisable material m the pile and a spatial distribution of IOP s of o disable material in the pile; and
(v) adjusting ihe opeiating conditions oi Ihe pile
l ' The n eihod oj < 1 n"in 17
Figure imgf000035_0001
.tn the at l ist ne piopcrly of the in iicrnl i-. .! .-*• ic 1 i >m ie τ'«πp • on i im- oi niji - . «ι_ " ι p .i n r d'-i hi ull ia eom .ni I 'i P i l i i L? 111 ΌII i n ι h- e
19 The method of claim 17 wherein the model is a computer model based on a deterministic fon ulation of multiphase flow through porous media.
20. The method of claim 17 wherein the step of adjusting includes a process selected from the group consisting of aerating the pile and contacting the pile of material with a liquid selected from the group consisting of water and an aqueous liquid.
21. A system for determining a rate of change in gaseous oxygen concentration within of a pile of material, said pile of material comprising both solid phase and gas phase, said system comprising:
(i) means for altering the gaseous oxygen concentration in at least a part of a pile of material; (ii) means for measuring the gaseous oxygen concentration within the pile of material; (iii) means for repeating the measuring of the gaseous oxygen concentration within the pile of material; (iv) means for determining the rate of change in the gaseous oxygen concentration.
22. The system of claim 21 wherein the means for altering comprises means for passing a gas containing oxygen through said at least part of said pile, and means for stopping said passing.
23. The system of claim 21 further comprising:
(v) means for delermining the time at which the measuring occurred; and
(vi) means for delermining an intrinsic oxidation rate at a location within the pile.
24. A system for determining a rate of change in gaseous oxygen concentration withm of a pile of material said pile of material comprising both solid phase and g ς ph.-rc, aid ""slem computing:
(i) m ιtι Hoi J iι di i nm ihe g i r »n y_"iι e me :u1ι Hi n in ι 1: J.I μ iu.l
Figure imgf000036_0001
(tit all o Jen in. jϋind. ι_*- fnι in., TMiii inc ' -i »"onr _'eu c me.im aι> n within the pile of matenal; (iii) a controlling device for repeating the measuring of the gaseous oxygen concentration within the pile of material; (iv) a computer for determining the rate of change in the gaseous oxygen concentration.
25. A system for determining a spatial distribution of rates of change in gaseous oxygen concentration within a pile of material, said pile of material comprising both solid phase and gas phase, said system comprising:
(i) a plurality of probes capable of being located in the pile;
(ii) means for altering the gaseous oxygen concentration surrounding at least two of said probes; (iii) means for measuring the gaseous oxygen concentration in the gas surrounding the at least two of said probes in the pile;
(iv) means for determining the rate of change in gaseous oxygen concentration of the gas surrounding said at least two of said probes in the pile; and
(v) means for determining a spatial distribution of rates of change in gaseous oxygen concentration in the pile.
26. The system of claim 25 wherein said means for altering comprises means for passing a gas containing oxygen through the location of the at least two of said probes, and means for stopping said altering
27. The system of claim 25 comprising means for detennining a spatial distribution of IORs within the pile.
2υ The syJem oi claim 25 ndiereui inoie than one probe is connected lo a pariieular means for measuring and there is additionally means to selectively dnect gas horn i piobc connected rhei eio m ihe p i ncular mean-, lor ni aeurπa- n ^ii" pirttcnl ai
2" ^ _ ' . in ioi s lcl .i nimu ij > p π 4 l ι ι ιbπn« »u l ι t o i i m " . in _ r> H oxygen concentration withm a pile of material, said pile oi material compnsmg both solid phase and gas phase, said system compnsing: (i) a plurality of probes capable of being located in the pile; (ii) at least two aerators for altering the gaseous oxygen concentration surrounding at least two of said probes; (iii) an oxygen measuring device for measuring the gaseous oxygen concentration in the gas surrounding the at least two of said probes in the pile; (iv) a computer for determining the rate of change in gaseous oxygen concentration of the gas surrounding said at least two of said probes in the pile; and (v) a computer for determining a spatial distribution of rates of change in gaseous oxygen concentration in the pile.
30. A system for controlling the operating conditions of a pile of material, said pile of material comprising both solid phase and gas phase, comprising:
(i) means for determining information selected from an IOR of oxidisable material in the pile and a spatial distribution of IORs in the pile; and (ii) means for adjusting at least one operating condition of the pile.
31. The system of claim 30 wherein the means for adjusting comprises means selected from the group consisting of means for aerating the pile and means for contacting the pile of material with a liquid selected from the group consisting of water and an aqueous liquid.
32. The system of claim 30 wherein the means for adjusting is capable of adjusting the operating conditions selectively in different portions of the pile.
33. A system for controlling the operating conditions of a pile of material, said pile of material comprising both solid phase and gas phase, comprising:
(i) a system according to claim 23 for deleiniining information selected from an IOR of oxidisable material in the pile and a spatial distribution ot IORs in the pile -and
.-* e' i« e "dec led horn ihe vn itp -I'l.M.atny ol' an aei sior and nt m i rioi loi itjjι«rιinr, . '■ ie "i oi i pei mi c. cn n ' n '"»ι i e pile
PCT/AU2004/000151 2003-02-11 2004-02-11 Measuring rate of change of oxygen concentration and intrinsic oxidation rate in a pile of material WO2004072636A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2004210879A AU2004210879A1 (en) 2003-02-11 2004-02-11 Measuring rate of change of oxygen concentration and intrinsic oxidation rate in a pile of material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2003900604A AU2003900604A0 (en) 2003-02-11 2003-02-11 Methods and Systems for Measuring Rate of Change in Gaseous Oxygen Concentration and for Measuring Intrinsic Oxidation Rate in a Pile of Material
AU2003900604 2003-02-11

Publications (2)

Publication Number Publication Date
WO2004072636A1 true WO2004072636A1 (en) 2004-08-26
WO2004072636A9 WO2004072636A9 (en) 2004-11-11

Family

ID=30005304

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2004/000151 WO2004072636A1 (en) 2003-02-11 2004-02-11 Measuring rate of change of oxygen concentration and intrinsic oxidation rate in a pile of material

Country Status (2)

Country Link
AU (1) AU2003900604A0 (en)
WO (1) WO2004072636A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013017162A1 (en) * 2011-08-01 2013-02-07 Endress+Hauser Conducta Gesellschaft Für Mess- Und Regeltechnik Mbh+Co. Kg Arrangement for the in-situ measurement of at least the oxygen content within a solid waste dump
WO2018068087A1 (en) * 2016-10-10 2018-04-19 Commonwealth Scientific And Industrial Research Organisation Apparatus, method and system for monitoring
CN111192628A (en) * 2020-02-27 2020-05-22 西安理工大学 Oxygen diffusion coefficient calculation method of polydimethylsiloxane
CN112051386A (en) * 2020-09-16 2020-12-08 西南民族大学 Soil methane detection device and method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6083790A (en) * 1989-08-09 1991-02-14 Steffen, Robertson And Kirsten Australasia Pty Limited Oxidation of mineral heaps
US6036862A (en) * 1998-01-20 2000-03-14 Stover; Enos L. Biochemically enchanced thermophilic treatment process
WO2001018269A1 (en) * 1999-09-07 2001-03-15 Billiton Intellectual Property B.V. Recovery of copper from copper bearing sulphide minerals by bioleaching with controlled oxygen feed
WO2001031072A1 (en) * 1999-10-28 2001-05-03 Mintek A method of operating a bioleach process with control of redox potential

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6083790A (en) * 1989-08-09 1991-02-14 Steffen, Robertson And Kirsten Australasia Pty Limited Oxidation of mineral heaps
US6036862A (en) * 1998-01-20 2000-03-14 Stover; Enos L. Biochemically enchanced thermophilic treatment process
WO2001018269A1 (en) * 1999-09-07 2001-03-15 Billiton Intellectual Property B.V. Recovery of copper from copper bearing sulphide minerals by bioleaching with controlled oxygen feed
WO2001031072A1 (en) * 1999-10-28 2001-05-03 Mintek A method of operating a bioleach process with control of redox potential

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BENNETT J. W. ET AL.: "Comparison of oxidation rates of sulfidic mine wastes measured in the laboratory and field", AUSTRALIAN CENTRE FOR MINING ENVIRONMENTAL RESEARCH, February 2000 (2000-02-01), BRISBANE, pages 2-7 - 51-53 *
DATABASE WPI Week 199114, Derwent World Patents Index; AN 1991-094597 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013017162A1 (en) * 2011-08-01 2013-02-07 Endress+Hauser Conducta Gesellschaft Für Mess- Und Regeltechnik Mbh+Co. Kg Arrangement for the in-situ measurement of at least the oxygen content within a solid waste dump
US9518922B2 (en) 2011-08-01 2016-12-13 Endress+Hauser Conducta Gmbh+Co. Kg Arrangement for in situ measurement of at least the oxygen content within a solids heap
WO2018068087A1 (en) * 2016-10-10 2018-04-19 Commonwealth Scientific And Industrial Research Organisation Apparatus, method and system for monitoring
CN109937460A (en) * 2016-10-10 2019-06-25 联邦科学及工业研究组织 Device, method and system for monitoring
RU2743487C2 (en) * 2016-10-10 2021-02-19 Коммонвелт Сайентифик Энд Индастриал Рисерч Организейшн Device, method and system of monitoring
AU2017343674B2 (en) * 2016-10-10 2022-06-23 Commonwealth Scientific And Industrial Research Organisation Apparatus, method and system for monitoring
AU2017343674C1 (en) * 2016-10-10 2022-09-15 Commonwealth Scientific And Industrial Research Organisation Apparatus, method and system for monitoring
CN109937460B (en) * 2016-10-10 2023-04-21 联邦科学及工业研究组织 Device, method and system for monitoring
CN111192628A (en) * 2020-02-27 2020-05-22 西安理工大学 Oxygen diffusion coefficient calculation method of polydimethylsiloxane
CN111192628B (en) * 2020-02-27 2023-03-24 西安理工大学 Oxygen diffusion coefficient calculation method of polydimethylsiloxane
CN112051386A (en) * 2020-09-16 2020-12-08 西南民族大学 Soil methane detection device and method
CN112051386B (en) * 2020-09-16 2022-07-01 西南民族大学 Soil methane detection device and method

Also Published As

Publication number Publication date
AU2003900604A0 (en) 2003-02-27
WO2004072636A9 (en) 2004-11-11

Similar Documents

Publication Publication Date Title
Strömberg et al. Kinetic modelling of geochemical processes at the Aitik mining waste rock site in northern Sweden
Devol et al. A model for coupled sulfate reduction and methane oxidation in the sediments of Saanich Inlet
Scranton et al. Temporal changes in the hydrography and chemistry of the Cariaco Trench
Harries et al. The use of temperature profiles to estimate the pyritic oxidation rate in a waste rock dump from an opencut mine
Benstead et al. Direct mass spectrometric measurement of gases in peat cores
WO2004072636A1 (en) Measuring rate of change of oxygen concentration and intrinsic oxidation rate in a pile of material
Sracek et al. Comparison of methods for the estimation of pyrite oxidation rate in a waste rock pile at Mine Doyon site, Quebec, Canada
CN103858006B (en) For the device of in-site measurement at least oxygen content in solid heap
AU2004210879A1 (en) Measuring rate of change of oxygen concentration and intrinsic oxidation rate in a pile of material
EP1181547B1 (en) Apparatus for analysing reduced inorganic sulfur
Hess et al. Assessing seawater/basalt exchange of strontium isotopes in hydrothermal processes on the flanks of mid-ocean ridges
Van Den Berg et al. Redox processes in recent sediments of the river Meuse, The Netherlands
House et al. Chemical modelling applications to experimental recirculating streams
JP6449757B2 (en) Test apparatus and test method
Aylmer et al. A new method for the simultaneous determination of pyrite content and proximate analysis in coal
Villaescusa et al. Development of a corrosivity classification for cement grouted cable strand in underground hard-rock mining excavations
Pearce et al. Instrumentation in waste rock dumps: Going deeper
Czerewko et al. The effects of storage conditions on the sulphur speciation in geological material
JP5013419B2 (en) Elution element collection device from rock
Kohfahl et al. Rising groundwater tables in partly oxidized pyrite bearing dump-sediments: Column study and modelling approach
Tan et al. In situ determination of thermal conductivity of waste rock dump material
Brendel Development of a mercury thin film voltammetric microelectrode for the determination of biogeochemically important redox species in porewaters of marine and freshwater sediments
Vernon Development of geophysical techniques for studying early iron smelting sites
US20220334096A1 (en) Monitoring of concrete curing
Mountjoy et al. Construction, Instrumentation and Preliminary Results of Field Leach Pads for Scaling Reaction Rates and Assessing Field Performance

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
COP Corrected version of pamphlet

Free format text: DUE TO A SCANNING ERROR DURING THE TECHNICAL PREPARATIONS FOR INTERNATIONAL PUBLICATION, REPLACE ALL PAGES (INCLUDING FRONT PAGE) BY CORRECT PAGES (47 PAGES)

WWE Wipo information: entry into national phase

Ref document number: 2004210879

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2004210879

Country of ref document: AU

Date of ref document: 20040211

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 2004210879

Country of ref document: AU

122 Ep: pct application non-entry in european phase