CA2277622C - Autoclave having high oxygen transfer rate to metal-containing solutions - Google Patents

Autoclave having high oxygen transfer rate to metal-containing solutions Download PDF

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Publication number
CA2277622C
CA2277622C CA002277622A CA2277622A CA2277622C CA 2277622 C CA2277622 C CA 2277622C CA 002277622 A CA002277622 A CA 002277622A CA 2277622 A CA2277622 A CA 2277622A CA 2277622 C CA2277622 C CA 2277622C
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metal
gas
oxygen
slurry
autoclave
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CA2277622A1 (en
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James A. King
Jinxing Ji
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Placer Dome Technical Services Ltd
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Placer Dome Technical Services Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04Pressure vessels, e.g. autoclaves
    • B01J3/042Pressure vessels, e.g. autoclaves in the form of a tube
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20Mixing gases with liquids
    • B01F23/23Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/233Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements
    • B01F23/2331Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the introduction of the gas along the axis of the stirrer or along the stirrer elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20Mixing gases with liquids
    • B01F23/23Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/233Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements
    • B01F23/2331Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the introduction of the gas along the axis of the stirrer or along the stirrer elements
    • B01F23/23311Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the introduction of the gas along the axis of the stirrer or along the stirrer elements through a hollow stirrer axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20Mixing gases with liquids
    • B01F23/23Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/233Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements
    • B01F23/2331Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the introduction of the gas along the axis of the stirrer or along the stirrer elements
    • B01F23/23314Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the introduction of the gas along the axis of the stirrer or along the stirrer elements through a hollow stirrer element
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20Mixing gases with liquids
    • B01F23/23Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/233Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements
    • B01F23/2336Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the location of the place of introduction of the gas relative to the stirrer
    • B01F23/23363Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using driven stirrers with completely immersed stirring elements characterised by the location of the place of introduction of the gas relative to the stirrer the gas being introduced above the stirrer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053Details of the reactor
    • B01J19/0066Stirrers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/20Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • B01J8/22Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
    • B01J8/222Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid in the presence of a rotating device only
    • 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
    • C22B3/02Apparatus therefor
    • 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
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/11Stirrers characterised by the configuration of the stirrers
    • B01F27/112Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades
    • B01F27/1121Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades pin-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/11Stirrers characterised by the configuration of the stirrers
    • B01F27/113Propeller-shaped stirrers for producing an axial flow, e.g. shaped like a ship or aircraft propeller
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/11Stirrers characterised by the configuration of the stirrers
    • B01F27/19Stirrers with two or more mixing elements mounted in sequence on the same axis
    • B01F27/192Stirrers with two or more mixing elements mounted in sequence on the same axis with dissimilar elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00548Flow
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Combustion & Propulsion (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The autoclave of the present invention includes an impeller having a conduit to recirculate or introduce an oxygen-containing gas into the slurry. The outlets for the gas can be located in the blades of the impeller for thorough dispersion of the gas bubbles in the slurry.

Description

AUTOCIrAVB BlIVI~Tt3 HIGB OBYG$N
TRADTSFBB BlITB TO 1LBTlIL-CO~tTAI~TI~TG BOLOTIONB
FIELD OF THE INVENTION
The present invention ie generally directed to autoclaves and specifically to autoclaves having high rates of oxygen transfer to metal-containing solutions.
BACKGROUND OF THE INVENTION
To oxidize sulfide sulfur and thereby permit solubilization and/or liberation of metals compounded with the sulfide sulfur, base metal ores and concentrates, and refractory gold ores and Concentrates are commonly treated by pressure oxidation. Pressure oxidation is typically performed by passing a feed slurry of a metal-containing material through a sealed autoclave (operating at superatmospheric pressure) having multiple compartments. To provide for oxidation of the sulfide sulfur in the slurry, oxygen is typically fed continuously to the autoclave by means of a sparge tube located below the impeller. Commonly a large portion of the oxygen reacts with the sulfide sulfur, but there is a smaller significant portion that is vented from the autoclave and may be considered not effectively utilized.
In designing an autoclave, there are a number of considerations. By way of example, the autoclave should permit reaction of as much of the oxygen as possible with sulfide sulfur. If the oxygen is inefficiently reacted with the sulfide sulfur, the autoclave can have higher oxygen plant capital and operating costs. The autoclave should provide as short a residence time as possible for a given volume of slurry while realizing a high rate of recovery for the metal.
Finally, the autoclave should vent inert gases that build up in the autoclave above the slurry to prevent rupturing of the autoclave from high pressure gas. Some oxygen gas is inevitably vented along with these inert gases. Other processes, which rely on efficient and effective gas/liquid transfer of oxygen and which are commonly carried out in autoclaves, include catalytic chemistry reactions, such as the conversion of ferrous to ferric ions, reoxidation of NO by oxygen, and cuprous amine conversion to cupric amine.
SU1~IARY OF THE INVENTION
These and other design objectives are satisfied by the autoclave of the present invention. The autoclave includes a vessel for containing a feed slurry material, such as a metal sulfide-containing slurry, or a liquid comprising dissolved chemical compounds and an impeller attached to a rotatable shaft for agitating the feed slurry material. The shaft has a passage for an oxygen-containing gas and an outlet in communication with the passage for dispersing the oxygen-containing gas in the slurry. In one configuration, the passage passes along the length of the rotatable shaft, and the outlet is located at or close to the tip of the impeller.
-2-The autoclave can realize relatively high oxygen transfer rates to the feed slurry material relative to conventional autoclaves through better oxygen gas dispersion in the feed slurry material. Commonly, the autoclave can yield an oxygen transfer rate of at least about 2 kg moles oxygen/cubic meter of slurry/hour. At such high oxygen transfer rates, a high rate of metal recovery can be realized in a relatively short residence time, and therefore lower capital and operating costs for the autoclave equipment can be realized relative to conventional pressure oxidation processes.
The autoclave is able to accomplish such high oxygen transfer rates without the use of a sparge tube. The sparge tube has proven to be an ongoing source of maintenance problems in existing pressure oxidation processes.
To consume as much oxygen as possible, the rotatable shaft can have an inlet for the oxygen containing gas located at an upper end of the shaft that is above the slurry surface yet is contained within the vessel. The inlet will provide a suction, drawing the atmosphere in the autoclave into the 2o passage. After passing through the passage, the gas is dispersed into the feed slurry material. In this manner, the oxygen is continuously recycled during pressure oxidation to provide a high rate of oxygen utilization. By efficiently reacting the oxygen, the autoclave can have lower oxygen plant capital and operating costs than conventional autoclaves.
-3-New oxygen can be supplied to the autoclave either directly through the rotatable shaft or through a separate conduit such as one having an outlet in close proximity to the impeller shaft gas inlet or above the feed slurry material.
In the latter case, the shaft must include the inlet at the upper end of the shaft to permit oxygen escaping from the agitated feed slurry material into the autoclave atmosphere and/or supplied to the atmosphere to be drawn into the shaft and thereby entrained in the agitated feed slurry material.
The rotatable shaft of the present invention can provide improved reaction rates in the upstream compartments of the autoclave. In conventional autoclaves, the initial compartments frequently operate at a temperature below the desired operating range (which is from about 180oC to about 220oC) because the exothermic conversion of sulfides to sulfates in the initial compartments is insufficiently complete to raise the temperature to the desired operating range. To raise the temperature to within this range, it is common to add steam (from a source external to the autoclave) to the initial compartments to raise the temperature of the slurry in the compartment and thereby increase the rate of conversion of sulfides to sulfates. Steam can be costly to add to the system. In contrast, in the autoclave of the present invention the rotatable shaft draws steam in the autoclave atmosphere through the shaft and into the slurry in the initial compartments, thereby providing a higher
-4-temperature in the slurry in these compartments and a concomitant higher reaction rate. In other words, the rotatable shaft increases the heat transfer from the discharge end of the autoclave (i.e., the downstream compartments) to the input end of the autoclave (i.e., the upstream compartments). Accordingly, the autoclave of the present invention can be less expensive to operate than conventional autoclaves that inject steam into the initial compartments.
Autoclaves can include a discharge control means for controllably removing the gas atmosphere from the sealed autoclave to prevent rupture of the autoclave from high pressure gases. The system includes:
(a) analyzing means (e.g., a gas analyzer) for analyzing a selected component (e. g., carbon dioxide and/or molecular oxygen) in the gas atmosphere inside the autoclave;
(b) an outlet for removing gas in the gas atmosphere from the autoclave interior:
(c) a controller (e.g., a computer) for receiving a signal from the gas analyzer and generating a control signal in response thereto: and (c) a control means (e.g., a valve) for controlling the amount of gas removed in response to the control signal received from the controller. The control means vents the gas atmosphere when the amount of the component exceeds or falls below a threshold amount. In this manner, the autoclave can vent oxygen gas and other gases that build up in the autoclave
-5-above the slurry while maintaining the oxygen gas in the autoclave as long as possible for consumption in the oxidation of sulfide sulfur.
In operation, pressure oxidation using the autoclave follows the following steps:
(a) agitating a feed slurry material in the autoclave using the impeller, and (b) during the agitating step (a), passing an oxygen-containing gas through the rotatable shaft and dispersing the gas radially outward from the shaft into the feed slurry material. In one autoclave configuration, the gas is passed through a blade of the impeller outwardly into the slurry.
In another embodiment of the invention, the impeller is used in conjunction with a sparge tube to provide a further increase in the oxygen content of the feed slurry material.
The sparge tube is preferably located in the vicinity of the impeller and more preferably is located beneath the impeller such that bubbles of the oxygen-containing gas released by the sparge tube are dispersed in the vessel by the impeller.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 depicts a side view of the interconnected impeller and the rotatable shaft of the agitation assembly, with certain parts of the agitation assembly being shown in cross-section;
-6-Fig. 2 is a cross-sectional view taken along line 2-2 of Fig. 1~
Fig. 3 depicts the agitation assembly operating in an autoclave Fig. 4 is a flow schematic depicting the discharge control systems Fig. 5 is a cross-sectional view of an autoclave of the present invention showing the various compartments: and Fig. 6 is a latitudinal cross-sectional view of an autoclave containing an EIiATO agitator used in the experiments.
DETAILED DESCRIPTION
The present invention is directed to a sealed autoclave particularly useful for pressure oxidation of slurried ores and concentrates. Although the autoclave is discussed with reference to leaching processes, the autoclave is useful in numerous other applications including catalytic chemistry reactions. The autoclave includes an agitation assembly for 2o discharging oxygen directly into the slurry. In this manner, the autoclave is able to realize relatively high rates of oxygen transfer into the slurry and, therefore, high oxidation rates and low residence times. The autoclave is particularly effective in the pressure oxidation of slurried metal sulfide-containing materials. The metal sulfides that can be effectively utilized include without limitation gold sulfides, iron sulfides, copper sulfides, zinc sulfides, nickel sulfides, and arsenic sulfides.
Referring to Figs. 1 and 2, the agitation assembly 10 is depicted. The agitation assembly 10 includes a rotatable shaft 14, a gas injecting impeller 18 and a mixing impeller 22 connected to the lower end of the shaft 14, and a motor (not shown) connected to the upper end of the shaft 14 for rotating the shaft 14 during pressure oxidation.
The rotatable shaft 14 includes a gas inlet 26 in communication with a conduit 30 extending longitudinally along the shaft 14. The conduit 30 is in communication with a number of conduits 34a-d in the gas injecting impeller 18 for dispersing the gas substantially uniformly throughout the slurry. A fresh oxygen-containing gas 37 from an oxygen supply plant or the ambient atmosphere can be introduced to the slurry via an inner conduit 25, the conduit 30, and finally radially outward through the conduits 34a-d. An oxygen-containing gas 38 is recycled from the autoclave atmosphere via inlet 26 (which is open to the autoclave interior) because rotation of the impeller 18 creates a negative pressure at the tips 78 a-d of the blades which draws the gas through the inlet 26. The fresh oxygen-containing gas 37 mixes with the recycled oxygen-containing gas 38 downstream (or below) the outlet 39 of the inner conduit 25 and the mixed gas is outputted by the conduits 34 a-d.
-g-The relative orientations and dimensions of the inlet 26 and shaft conduit 30 are important. The longitudinal axis 42 of the conduit 30 is substantially normal (i.e., transverse) to the longitudinal axis 46 of the inlet 26. The conduit 30 and shaft 14 are coaxial and therefore have the same longitudinal axis 42. The relationship between the cross-sectional area of the inlet 26 normal to the direction of flow (i.e., normal to the inlet longitudinal axis 46) depends upon a number of factors including the desired oxygen transfer rate, the compartment size of the autoclave, the operating oxygen partial pressure, the slurry viscosity, and the like.
The bottom 62 of the conduit 30 is may be comically shaped in a convex orientation to effectuate redirection of the gas into the conduits 34a-d of the impeller 18. In this manner, eddies and other disturbances in the gas flow in response to the sudden change of direction are substantially minimized.
To facilitate dispersion of the gas in the slurry, the gas injecting impeller 18 has the outlet face 74a-d of each impeller blade 70a-d angled away from the direction of rotation of the gas injecting impeller 18 such that a shear zone exists at the tip 78a-d of each blade 70a-d to provide superior atomization and dispersion of the oxygen-containing gas (and therefore finer bubble formation). The outlet face 74a-d of each conduit 34a-d faces away from the direction of rotation while the longest side of the blade 70a-d faces in .g-the direction of flow. The angle between the outlet face 74a-d and the tangent 82 of a circle defined by rotation of the tips 78a-d of the blades 70a-d is preferably about forty-five degrees.
The gas injecting impeller 18 is located at a depth in the autoclave slurry that maximizes effective gas transfer and dispersion. Locating the impeller below this optimum depth increases the hydraulic head that the impeller has to overcome to draw down the gas phase into the agitated slurry. This can significantly and unnecessarily increase the power required to maintain a given oxygen transfer rate.
The mixing impeller 22 is located below the gas injecting impeller 18 at a suitable depth to maintain in suspension the solid particles in the autoclave in the slurry and to assist in distribution of the entrained gas bubbles in the slurry.
Typically, the concentration of gas bubbles in the upper portion of the slurry (which contains the gas-injecting impeller 18) is greater than the gas bubble concentration in the lower portion of the slurry (which contains the mixing impeller 22).
Referring to Fig. 3, the operation of the agitation assembly will be described. During introduction of the sulfide-containing slurry 86 into the autoclave 90, the rotatable shaft 94 is rotated in a clockwise direction to induce turbulence in the slurry. Unlike the rotatable shaft 14 of Figs. 1 and 2, the rotatable shaft 94 of Fig. 3 has a plurality of open inlets 98 that are open to the atmosphere in the autoclave 90 and an inner conduit extending the length of the shaft 94 to transport fresh oxygen gas from a source exterior to the autoclave. Rather, fresh oxygen 106 is introduced directly into the autoclave atmosphere via inlet 91 and drawn into the open inlets 98 and through a conduit (not shown) extending longitudinally along the shaft and finally through the blades and dispersed into the slurry. A vortex 102 forms where the shaft 94 is immersed in the slurry 86. An oxygen gas 106 is introduced into the autoclave and mixed with recirculated gas 110 drawn into the shaft via the inlets 98.
The mixed gas 114 is dispersed radially outwardly, during rotation of the blades 70a-d, in the slurry 86. The mixing impeller 22, which rotates at the same rate and in the same direction as the gas injecting impeller 18, further assists in dispersing the gas bubbles 118 throughout the slurry 86, maintains in suspension the solid particles in the slurry, and provides a turnover of slurry from the bottom to the top of the vessel on a continuous basis.
The autoclave 90 is able to realize high oxygen transfer rates into the slurry 86. Typically, the oxygen transfer rate is at least about 2kg moles and more typically at least about 4 kg moles and most typically ranges from about 2 kg moles to about 12 kg moles of molecular oxygen/cubic meter of slurry/hour. At such high transfer rates, the conversion of the metal sulfides into soluble metal salts or oxidized metal precipitates can be substantially completed (i.e., 90% or more) in residence times as short as about 60 minutes and more typically in as short as about 30 minutes.
Fig. 4 depicts a discharge control system for controllably removing the gas atmosphere from the autoclave 90 to prevent rupture of the autoclave 90 from high pressure gases. The system 130 includes a gas analyzer 134 for analyzing, either continuously or at suitable intervals of time, a selected component in the gas atmosphere in the autoclave 90, a vent 138 for venting the gas in the atmosphere, a controller 142 to monitor the signal 144 from the gas analyzer 134 and generate a control signal 146 in response thereto, and a control device 150 for controlling the amount of gas discharged into the exterior atmosphere in response to the control signal 146.
The selected component monitored by the gas analyzer 134 can be molecular oxygen, carbon dioxide, argon, and nitrogen, with molecular oxygen being most preferred.
When a threshold concentration, or partial pressure, of the selected component is reached, the controller 142 forwards a control signal to the control device 150 to open and release gas in the autoclave atmosphere. Preferably, the threshold is set such that the ratio of the partial pressure of oxygen to the partial pressure of nonoxygen compounds (e. g., carbon dioxide) ranges from about 1:4 to about 4:1 and more preferably from about 1:2 to about 2:1. Accordingly, when the partial pressure of oxygen drops below a certain level, i.e., when the ratio falls below the threshold, the control device 150 opens and the autoclave gas phase is vented to the atmosphere. Fresh "pure" oxygen is introduced at this time to maintain the autoclave operating pressure setpoint. The control device 150 closes either after the valve has been opened for a specified predetermined time or alternately, may be closed when the partial pressure of oxygen is restored to a specified setpoint.
Referring to Figure 5, an autoclave 200 utilizing a plurality of rotatable shafts 94a-j according to the present invention is depicted. In the initial compartments 204a and 204b, the operating temperature of the slurry is within the desired operating range because steam in the autoclave atmosphere 208 above the slurry 202 is drawn through the shaft and injected into the slurry at or near the impeller (i.e., mixing blades). As a result, additional steam is not introduced into the initial compartments. The autoclave further includes an optional sparge tube 212a-j in each compartment 204a-j for additional oxygen enrichment of the slurry 202. As will be appreciated, superheated steam 220 from the downstream compartments is drawn to the upstream compartments where it is introduced into the slurry 202.
A vent 230 is located at the input end of the autoclave to release inert gases, such as carbon dioxide, nitrogen and argon. As will be appreciated, the atmosphere of the autoclave typically contains about 80% steam, 8% molecular oxygen, and 12% inert gases. The carbon dioxide is evolved by the destruction of carbonate minerals in the autoclave feed by the acid present in the autoclave oxidized slurry. Nitrogen and argon can be present as impurities in the oxygen supply.
The vent is preferably located to the input end of the autoclave because most of the carbon dioxide is evolved in the initial compartments. This location of the vent allows generally a higher carbon dioxide-to-oxygen ratio in the vent gas which substantially minimizes the overall oxygen consumption in the sulfur oxidation reaction.
EXPERIMENTAL
An experiment was performed using a type HWL2060~
standard agitator manufactured by EKATO~ of the type shown in Figure 6. The agitator included a plurality of open inlets 300 that were open to the atmosphere in the autoclave. The agitator did not have an inner conduit extending the length of the shaft to transport fresh oxygen gas from a source exterior to the autoclave into the slurry. The impeller blades 304 were made of round pipe. Alternatively, the blades could be made of square pipe, rectangular pipe, or any other shaped pipe. The blade tips 308 had an angle between the outlet face and the tangent of a circle defined by rotation of the tips of the blades 310 was about 450, though the angle could range from about 30 to about 600. The oxygen re-entrainment ports 300 of the agitator were located on the upper (hollow) shaft 312. The motor 316 and a gear unit 320 were located at the upper end of the agitator. An interprop 324 was located below the blades. Modifications can be made to allow pure oxygen being injected near or into these ports instead of sparging oxygen into the slurry. A RUSHTOIJ~ interprop agitator was also used by way of comparison to the EKATO~ agitator.
In two of the trials, a sparge tube was used with the agitator to determine if the two oxygen introduction devices would synergistically provide even higher oxygen transfer rates compared to either device when used alone.
Data were measured in a solution containing about 0.5 M
sodium sulfite and 6 ppm cobalt. Oxygen partial pressure was about 50 psi and the starting total pressure was about 386 psig at ambient temperature. The diameter of the agitator was about 980 mm and the pressure vessel volume was around 5 cubic meters.

TABLE OF TEST RESULTS
0.5 M NaZS03, 6 ppm Co2+, 50 psi O2, Total Pressure = 386 psig, ambient temperature, 980 mm ERATO gassing impeller, 5 m' pressure vessel Top Type Type of Oxygaa 7~gitator oxygen Oxygen of ImpellerTop Bottom SpargingBower DrswTransfer Transfer Depth ImpellerImpeller Rats Energy Requirement (kW) (kg/m'.h) (kW.h/t-02) 700 RUSHTONeInterpropNO 14.4 39 87.6 700 NO 5.5 50 26.7 ~

E1CAT0 Interprop -Gassing 13.6 100 32.7 20.8 209 23.9 500 5.3 72 17.8 e ERATO Iaterprop Gassing 13.7 92 35.9 21.1 145 34.8 500 ERATO~ Pitch YES 6.3 87 17.3 Gassin Dower g Turbine 15.6 270 13.8 500 ERATO~ RU8HTOIJ~YE8 6.4 114 13.5 Gassing Turbine 16.5 273 14.5 As can be seen from the table, the oxygen transfer rate was high in a number of the experiments, particularly when a sparge tube was used with the impeller. To realize the same benefits of sparging, the agitator design-of Figure 2 could also be employed.
While carious embodiments of the present invention have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the scope of the present invention, as set forth in the following claims.

Claims (56)

What is claimed is:
1. An autoclave for leaching metal from a metal-containing material, comprising:
a vessel for containing a slurry comprising the metal-containing material, the vessel being seated from the exterior atmosphere and operating at superatmospheric pressure; and an impeller attached to a rotatable shaft, the rotatable shaft comprising a passage for an oxygen-containing gas, an inlet in communication with the passage and a source for the oxygen-containing gas that is located outside of the vessel and outlets in communication with the passage for dispersing the oxygen-containing gas in the slurry.
2. The autoclave of Claim 1, wherein recycled oxygen-containing gas in the autoclave is contained in an upper portion of the vessel and the rotatable shaft comprises an inlet in communication with the passage and the upper portion of the vessel to transport the oxygen-containing gas from the upper portion of the vessel into the slurry.
3. The autoclave of Claim 1, wherein the rotatable shaft has an axis of rotation and the passage is disposed concentrically about the axis of rotation.
4. The autoclave of Claim 1, wherein the outlets are located at the impeller.
5. The autoclave of Claim 1, further comprising a gas discharge controller in communication with the vessel interior for discharging pressurized gas from the vessel interior at controlled rates.
6. The autoclave of Claim 5, wherein the gas discharge controller comprises:
(a) an analyzer for analyzing a component of the gas in the vessel interior, the analyzer means being in communication with the vessel interior;
(b) an outlet for removing gas from the gas atmosphere;
(c) a controlling device for controllably discharging the gas in the vessel interior into the exterior atmosphere through the outlet, the controlling device being in communication with the vessel interior; and (d) a controller, in communication with the analyzer and the controller, far providing a control signal to the controlling device in response to a signal received from the analyzer.
7. A method for recovering a metal from a metal-containing material by autoclaving, comprising:
(a) contacting the metal-containing material with a liquid to form a metal-containing slurry;
(b) agitating the metal-containing slurry in a sealed vessel using an impeller engaging a rotatable shaft, wherein the rotatable shaft comprises an inlet in communication with a passage for an oxygen-containing gas and a source for the oxygen-containing gas that is located outside the vessel;
(c) during the agitating step (b), passing an oxygen-containing gas through the rotatable shaft and dispersing the gas radially outward from the shaft into the slurry; and (d) thereafter recovering the metal from the metal-containing slurry.
8. The method of Claim 7, wherein step (c) further comprises passing the gas through a blade of the impeller.
9. The method of Claim 7, wherein step (c) further comprises:
measuring a selected component of a gas atmosphere in the sealed vessel, the gas atmosphere being located above the metal-containing slurry; and when the amount of the component exceeds or falls below a threshold amount, removing at least a portion of the gas atmosphere from the sealed vessel.
10. The method of Claim 9, wherein the selected component is selected from the group consisting of molecular oxygen, carbon dioxide, argon, and nitrogen.
11. The method of Claim 9, wherein the rate of removal of the gas atmosphere varies over time.
12. An autoclave for leaching metal from a metal-containing material, comprising:
a sealed vessel for containing a slurry comprising the metal-containing material;
rotatable shaft at least partially contained within the sealed vessel, the rotatable shaft having a passage extending along a substantial portion of the length of the shaft for transporting a gas from an upper end of the rotatable shaft to the lower end of the rotatable shaft, the passage further including an inlet located at the upper end of the rotatable shaft and an outlet located at the lower end of the rotatable shaft; and an impeller mounted on a lower end of the rotatable shaft and having at least one blade having an impeller passage in communication with the passage in the rotatable shaft.
13. The autoclave of Claim 12, wherein, when a slurry is contained in the sealed vessel, the rotatable shaft transfers oxygen from an oxygen-containing gas to the slurry at a rate of at least 2 Kg moles oxygen/cubic meter of slurry/hour.
14. The autoclave of Claim 1, further comprising a sparge tube located in the vessel with the impeller, the sparge tube releasing the oxygen-containing gas into the slurry.
15. The method of Claim 7 further comprising releasing the oxygen-containing gas into the metal-containing slurry by a sparge tube.
16. A method for recovering a metal from a metal-containing material by autoclaving, the metal-containing material being contained in a slurry, comprising:
(a) agitating the metal-containing slurry in a sealed vessel using at least one impeller engaging a rotatable shaft;
(b) while agitating the slurry, passing a first oxygen-containing gas through the rotatable shaft and a second oxygen-containing gas through a sparge tube having an outlet located near the rotatable shaft and discharging the first and second oxygen-containing gases into the slurry; and (c) thereafter recovering the metal from the metal-containing slurry.
17. The method of claim 16 wherein step {b) comprises passing the gas through a blade of the impeller.
18. The method of claim 16 further comprising:
measuring a selected component of a gas atmosphere in the sealed vessel, the gas atmosphere being located above the metal-containing slurry and when the amount of the component exceeds or falls below a threshold amount, removing at least a portion of the gas atmosphere from the sealed vessel.
19. The method of claim 18 wherein the selected component is selected from the group consisting of molecular oxygen, carbon dioxide, argon, and nitrogen.
20. The method of claim 18 wherein the rate of removal of the gas atmosphere varies over time.
21. The method of claim 16 wherein the second gas is discrete from the first gas during the passing step (b).
22. A method for recovering a metal from a metal-containing material by pressure oxidation, the metal-containing material being contained in a slurry, comprising:
(a) agitating the slurry using an impeller having a rotatable shaft with a passage;
(b) while agitating the slurry, introducing first and second oxygen-containing gases into the slurry, the first oxygen-containing gas being introduced into the slurry through the passage in the impeller shaft, positioned at a first location in the slurry and the second oxygen-containing gas being introduced into the slurry at a second, different, location, whereby the metal in the metal-containing material is removed from the metal-containing material;
and (c) thereafter recovering the metal from the metal-containing slurry.
23. The method of claim 22 wherein the second oxygen-containing gas is passed through a sparge tube positioned in the slurry and having an outlet located near the rotatable shaft.
24. The method of claim 22 wherein the first oxygen-containing gas is passed through a blade of the impeller.
25. The method of claim 22 wherein the second oxygen-containing gas is discrete from the first gas during the introducing step (b).
26. A method for recovering a metal from a metal-containing material by pressure oxidation, the metal-containing material being entrained in a slurry, comprising:
(a) agitating the slurry with an impeller;
(b) while agitating the slurry, introducing first and second oxygen-containing gases of at least one of water vapor and carbon dioxide into the slurry, the first oxygen-containing gas being passed through a rotatable shaft of the impeller at a first location into the slurry and the second oxygen-containing gas being introduced into the slurry at a second, different, location whereby the metal is removed from the metal-containing material; and (c) thereafter recovering the removed metal from the metal-containing slurry.
27. The method of claim 26 wherein the second gas is passed through a sparge tube positioned in the slurry and having an outlet located near the impeller.
28. The method of claim 26 wherein the first gas is passed through a blade of the impeller.
29. The method of claim 26 wherein the second gas is discrete from the first gas during the introducing step (b).
30. A method for recovering a metal from a metal-containing material by autoclaving, comprising:
(a) providing an autoclave containing a metal-containing material in a metal-containing slurry and an agitation assembly;
(b) agitating the metal-containing slurry in the autoclave by rotating a rotatable shaft that is part of the agitation assembly, the rotatable shaft including (i) a first inlet located above the slurry surface for removing a recycled gas from the interior of the autoclave; (ii) a second inlet for a fresh oxygen-containing gas from a source external to the autoclave; (iii) a plurality of outlets extending outwardly from an intermediate portion of the shaft and located at intervals around the periphery of the shaft such that the, outlets rotate when the shaft rotates; (iv) a passage in the rotatable shaft connecting the first and second inlets with the plurality of outlets; and (v) a plurality of mixing blades located on an end portion of the shaft and below the plurality of outlets, wherein during the agitating step (b), an oxygen-containing gas that includes the recycled gas and fresh oxygen-containing gas is passed through the rotatable shaft and the plurality of outlets and dispersed radially outwardly from the shaft into the slurry; and (c) recovering the metal.
31. The method of claim 30 wherein the plurality of outlets are inclined inwardly towards the shaft and wherein the outermost edge of each outlet forms the leading edge of each of the plurality of outlets during shaft rotation.
32. The method of claim 30 wherein step (b) comprises:
measuring a selected component of a gas atmosphere in the autoclave, the gas atmosphere being located above the metal-containing slurry and when the amount of the component exceeds or falls below a threshold, removing at least a portion of the gas atmosphere from the autoclave.
33. The method of claim 32 wherein the selected component is selected from the group consisting of molecular oxygen, carbon dioxide, argon, and nitrogen.
34. The method of claim 32 wherein the rate of removal of the gas atmosphere varies over time.
35. The method of claim 30 wherein the plurality of blades are shorter than the plurality of outlets.
36. The method of claim 30 wherein step (b) includes combining the recycled gas and fresh oxygen-containing gas in the passage.
37. The method of claim 36 wherein the fresh gas includes molecular oxygen that has not yet been introduced into the autoclave.
38. The method of claim 30 wherein the metal is in the form of a sulfide and the metal is selected from the group consisting of gold, iron, copper, zinc, and nickel.
39. The method of claim 33 wherein the threshold is a ratio of the partial pressure of molecular oxygen to the partial pressure of non-oxygen compounds and is within a range of from 1:4 to 4:1.
40. The method of claim 30 wherein step (c) includes:
measuring a selected compound of a gas atmosphere in the autoclave;
when a ratio of a partial pressure of the selected compound to the partial pressure of another compound of the gas atmosphere is less than a threshold amount, opening an output to the autoclave to remove at least a portion of the gas atmosphere; and when the output has been open for a predetermined time or when the ratio is at a specified setpoint that is at or above the threshold amount, closing the output to the autoclave.
41. A method for recovering a slurried metal from a metal-containing material by autoclaving, comprising:
(a) providing an autoclave that includes a sealed vessel and an agitator located in the sealed vessel, the agitator including (i) at least a first inlet located above a surface of a slurried metal-containing material and in communication with the interior of the sealed vessel, the at least a first inlet removing a recycled gas including oxygen from the interior of the sealed vessel; (ii) a second inlet in communication with an oxygen source located outside of the sealed vessel, the second inlet providing a fresh gas including oxygen from the oxygen source; (iii) an outlet located below the surface of the slurried metal-containing material for introducing the recycled and fresh gases into the slurried metal-containing material; and (iv) a passage in a shaft of the agitator, the passage being in communication with the first and second inlets and the outlet;
(b) rotating the agitator to agitate the slurried metal-containing material, wherein during rotation of the agitator the recycled and fresh gases are passed through the outlet and into the slurried metal-containing material to facilitate oxidation of a metal-containing compound in the slurried metal-containing material; and (c) thereafter recovering the metal in the metal-containing material.
42. The method of claim 41 wherein the outlet includes a plurality of outlets inclined inwardly towards the shaft and wherein the outermost edge of each outlet forms the leading edge of each of the plurality of outlets during shaft rotation.
43. The method of claim 41 further comprising:
measuring a selected component of a gas atmosphere in the interior, the gas atmosphere being located above the metal-containing slurry and when the amount of the component exceeds or falls below a threshold, removing at least a portion of the gas atmosphere from the autoclave.
44. The method of claim 43 wherein the selected component is selected from the group consisting of molecular oxygen, carbon dioxide, argon, and nitrogen.
45. The method of claim 43 wherein the rate of removal of the gas atmosphere varies over time.
46. The method of claim 41 wherein a plurality of mixing blades located below the outlet are each shorter than the outlet.
47. The method of claim 41 wherein step (b) includes combining the recycled gas and fresh gas in the passage.
48. The method of claim 47 wherein the fresh gas includes molecular oxygen that has not yet been introduced into the autoclave interior.
49. The method of claim 43 wherein the threshold is a ratio of the partial pressure of molecular oxygen to the partial pressure of non-oxygen compounds and is within a range of from 1:4 to 4:1.
50. The method of claim 41 further comprising:
measuring a selected component of a gas atmosphere in the interior;
when the ratio of a partial pressure of the selected compound to the partial pressure of another compound of the gas atmosphere is less than a threshold amount, opening an output to the autoclave to remove at least a portion of the gas atmosphere; and when the output has been open for a predetermined time or when the partial pressure of the selected component is at a specified setpoint that is at or above the threshold amount, closing the output to the autoclave.
51. A method for recovering a metal from a slurried metal-containing material by autoclaving, comprising:
(a) providing an autoclave that includes a sealed vessel and an agitator located in the sealed vessel, the agitator including (c) at least a first inlet located above a surface of a slurried metal-containing material and in communication with the interior of the sealed vessel, the at least a first inlet removing a recycled gas including oxygen from the interior of the sealed vessel; (ii) a second inlet in communication with an oxygen source located outside of the sealed vessel, the second inlet providing a fresh gas including oxygen from the oxygen source; (iii) a plurality of outlets located below the surface of the slurried metal-containing material for introducing the recycled and fresh gases into the slurried metal-containing material; (iv) a passage in a shaft of the agitator, the passage being in communication with the first and second inlets and the plurality of outlets; and (v) an impeller engaging the shaft and located below the plurality of outlets;
(b) rotating the agitator to agitate the slurried metal-containing material wherein during rotation of the agitator the recycled and fresh gases are passed through the plurality of outlets and into the slurried metal-containing material to facilitate oxidation of a metal-containing compound in the scurried metal-containing material; and (c) thereafter recovering the metal in the metal-containing material.
52. An autoclave for leaching metal from a metal-containing material, comprising:
a vessel for containing a slurry comprising the metal-containing material, the vessel being sealed from the exterior atmosphere and operating at superatmospheric pressure;
an impeller attached to a rotatable shaft, the rotatable shaft comprising a passage for an oxygen-containing gas, an inlet in communication with the passage and a source for the oxygen-containing gas that is located outside of the vessel and outlets in communication with the passage for dispersing the oxygen-containing gas in the slurry; and a gas discharge controller in communication with a vessel interior for discharging pressurized gas from the vessel interior at controlled rates.
53. The autoclave of Claim 52, wherein the gas discharge controller comprises:
(a) an analyzer for analyzing a component of the gas in the vessel interior, the analyzer means being in communication with the vessel interior;
(b) an outlet for removing gas from the gas atmosphere;
(c) a controlling device for controllably discharging the gas in the vessel interior into the exterior atmosphere through the outlet, the controlling device being in communication with the vessel interior; and (d) a controller, in communication With the analyzer and the controller, for providing a control signal to the controlling device in response to a signal received from the analyzer.
54. A method for recovering a metal from a metal-containing material by autoclaving, comprising:
(a) contacting the metal-containing material with a liquid to form a metal-containing slurry;
(b) agitating the metal-containing slurry in a sealed vessel using an impeller engaging a rotatable shaft, wherein the rotatable shaft comprises an inlet in communication with a passage for an oxygen-containing gas and a source for the oxygen-containing gas that is located outside the vessel;
(c) during the agitating step (b), passing an oxygen-containing gas through the rotatable shaft and dispersing the gas radially outward from the shaft into the slurry;
measuring a selected component of a gas atmosphere in the sealed vessel, the gas atmosphere being located above the metal-containing slurry; and when the amount of the component exceeds or falls below a threshold amount, removing at least a portion of the gas atmosphere from the sealed vessel; and (d) thereafter recovering the metal from the metal-containing slurry.
55. The method of Claim 54, wherein the selected component is selected from the group consisting of molecular oxygen, carbon dioxide, argon, and nitrogen.
56. The method of Claim 55, wherein the rate of removal of the gas atmosphere varies over time.

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