AU626332B2 - Cyanide recovery process - Google Patents

Description

l 62 332 COMPLETE SPECIFICATION FOR OFFICE USE Application Number: Lodged: Complete Specification Priority: Class Int. Class Lodged: Accepted: Published: Related Art: TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: CYPRUS MINERALS COMPANY 9100 East Mineral Circle, Englewood, Colorado 80155, United States of America.

Adrian James GOLDSTONE and Terry Irwin MUDDER SMITH SHELSTON BEADLE 207 Riversdale Road Box 410) Hawthorn, Victoria, Australia 4 Actual Inventors: Address for Service: S Complete Specification for the invention entitled: CYANIDE RECOVERY PROCESS The following statement is a full description of this invention, including the best method of performing it known to us: Page 1 Our Ref: #4511 PS:BC:WB 27cyp Cyanides are useful materials industrially and have been employed in fields such as electro-plating and electro-winning of metals, gold and silver recovery from ores, treatment of sulfide ore slurries in flotation, tannery processes, etc. Due to environmental concerns, it is desirable to remove or destroy the cyanide present in the waste solutions resulting from such processes.

o Additionally, in view of the cost of cyanide, it is desirable to regenerate the cyanide for reuse.

15 Techniques for cyanide disposal or regeneration (recovery) in waste solutions include: ion exchange, oxidation by chemical or electrochemical means, and acidification-volatilization-reneutralization

(AVR).

The term cyanide recovery and regeneration are used interchangeably herein.

U.S. Patent No. 4,267,159 by Crits issued May 12, 1981, discloses a process for regenerating cyanide in spent aqueous liquor by passing the liquor through a bed of suitable ion exchange resin to segregate the cyanide.

25 U.S. Patent No. 4,708,804 by Coltrinari issued November 24, 1987, discloses a process for recovering cyanide from waste streams which includes passing the waste stream through a weak base anion exchange resin in order to concentrate the cyanide. The concentrated cyanide stream is then subjected to an acidification/volatilization process in order to recover the cyanide from the concentrated waste stream.

U.S. Patent No. 4,312,760 by Neville issued January 26, 1982, discloses a method for removing cyanides from waste water by the addition of ferrous bisulfite which forms insoluble Prussian blue and other reaction products.

U.S. Patent No. 4,537,686 by Borbely et al. issued August 27, 1985, discloses a process for removing cyanide from aqueous streams which includes the step of oxidizing the cyanide. The aqueous stream is treated with sulfur dioxide or an alkali or alkaline earth metal sulfite or bisulfite in the presence of excess oxygen and a metal catalyst, preferably copper. This process is preferably carried out at a pH in the range of 5 to 12.

U.S. Patent No. 3,617,567 by Mathre issued November 2, 1971, discloses a method for destroying cyanide anions in aqueous solutions using hydrogen peroxide (H 2 0 2 and a soluble metal compound catalyst, such as soluble copper, to increase the reaction rate.

The pH of the cyanide solution to be treated is adjusted o 00 a o with acid or base to between 8.3 and 11.

Treatments based on oxidation techniques have a oaao 20 number of disadvantages. A primary disadvantage is that no cyanide is regenerated for reuse. Additionally, reagent costs are high, and some reagents H 2 0 2 react with tailing solids. Also, in both the Borbely et al and Mathre processes discussed above, a catalyst, a a 25 such as copper, must be added.

0 U.S. Patent No. 3,592,586 by Scott issued July 13, 0°44 1971, describes an AVR process for converting cyanide wastes into sodium cyanide in which the wastes are 4 heated and the pH is adjusted to between about 2 and a. a30 about 4 in order to produce hydrogen cyanide (HCN). The a a 4 HCN is then reacted with sodium hydroxide in order to form sodium cyanide. Although the process disclosed in the Scott patent is described with reference to waste produced in the electro-plating industry, AVR processes have also been applied to spent cyanide leachate resulting from the processing of ores. Such spent -2r cyanide leachate typically has a pH greater than about 10.5 prior to its acidification to form HCN.

AVR processes employed in the mineral processing field are described in the two volume set "Cyanide and the Environment" (a collection of papers from the proceedings of a conference held in Tucson, Arizona, December 11-14, 1984) edited by Dirk Van Zyl, "Cyanidation and Concentration of Gold and Silver Ores," by Dorr and Bosqui, Second Edition, published by McGraw- Hill Book Company 1950, and "Cyanide in the Gold Mining Industry: A Technical Seminar," sponsored by Environment Canada and Canadian Mineral Processor, January 20-22, 1981. Another description of an AVR process can be found in "Canmet AVR Process for Cyanide Recovery and Environmental Pollution Control Applied to 0° 0Gold Cyanidation Barren Bleed from Campbell Red Lakes .Mines Limited, Balmerton, Ontario," by Vern M. McNamara, S°o oMarch 1985. In the Canmet process, the barren bleed was acidified with H 2

SO

4 to a pH level typically between 2.4 and 2.5. SO 2 and H 2

SO

3 were also suitable for use in the acidification.

AVR processes take advantage of the very volatile nature of hydrogen cyanide at low pH. In an AVR ac.. process, the waste stream is first acidified to a low pH 2 to 4) to dissociate cyanide from metal complexes and to convert it to HCN. The HCN is volatilized, o:o: usually by air sparging. The HCN evolved is then recovered, for example, in a lime solution, and the Streated waste stream is then reneutralized. A commercialized AVR method known as the Mills-Crowe method is described in Scott and Ingles, "Removal of Cyanide from Gold Mill Effluents," Paper No. 21 of the Canadian Mineral Processors 13 Annual Meeting, in Ottawa, Ontario, Canada, January 20-22, 1981.

A process using AVR to recover cyanide values from a liquid is described in Patent Cooperation Treaty -3-

I

r application PCT/AU88/00119, International Publication No. W088/08408, of Golconda Engineering and Mining Services PTY. LTD. The disclosed process involves treating a tailings liquor from a minerals extraction plant by adjusting the pH into the acid range to cause the format" n of free hydrogen cyanide gas. The liquid is then passed through an array of aeration columns arranged in stages so that the liquid flowing from one aeration column in a first stage is divided into two or more streams which are introduced into separate aeration columns in successive stages. In a recent paper describing the process, it was stated that plant shutdown would occur if pH went above 3.5. In a commonly assigned application, PCT/AU88/00303, International Publication No. W089, 081357, a process for clarifying liquors containinc suspended solids is.

disclosed. The feed slurry is acidified to a pH of 3 or lower. Flocculants are added to cause the formation SD flocs to enable the separation of the suspended solids from the liquor. The clarified liquor can then be used as a feedstock for the AVR process disclosed in the other commonly assigned application.

The AVR processes described in the Scott patent and the above-mentioned texts typically include the step of adjusting the pH of the spent cyanide stream to within the range from about 2 to about 4. There are several problems with such processes. These AVR processes are expensive due to the amount of acidifying agent required to lower the pH to within this range. Also, such processes require a substantial amount of base to reneutralize the waste stream after the volatilization of HCN and prior to disposal. Further, insoluble metal complexes form at the acid conditions employed in these processes. The above-mentioned references only disclose a treatment of barren bleed which typically results from Merrill-Crowe type cyanidation treatment of ore. This -4- I bleed does not contain solid tailings. Today many ores are treated by a carbon-in-leach or carbon-in-pulp cyanidation process. The tailings from such processes include the solid barren ore in the spent leachate.

Typically the tailing slurries contain about 30% to by weight solids and about 100 to 350 parts per million (ppm) cyanide. In the past, such tailings were typically impounded and the cyanide contained therein was allowed to degrade naturally. Due to environmental concerns about cyanide, such impoundment is not a desirable alternative in many situations. Therefore, it is often necessary to treat the material in some manner to decompose the cyanide. This is expensive due to the costs associated with the treatment, as well as 15 the loss of cyanide values which results.

a 0a Therefore, it would be advantageous to remove .oo 0o cyanide from a cyanide-containing waste stream in an 0 a a0 economical manner. Further, it would be advantageous to am, a o oprovide a process for treating cyanide-containing a a oa0 20 slurries which also contain ore tailings. It would be advantageous if the amount of cyanide present in the waste stream could be reduced. It would also be advantageous to regenerate the cyanide for reuse.

It has now been found that when the HCN is volatilized at pH ranges higher than those previously aa employed, significant advantages are achieved. For ota example, cost savings can be realized due to the reduced amounts of reagents required to acidify and subsequently raise the pH of the waste stream. Additionally, many a 00 30 insoluble complexes which form under strong acid conditions will not form in the pH range employed in the oorr present process. Further, the higher pH avoids or minimizes scaling, for example, by calcium sulfate and/or metal thiocyanates such as copper thiocyanate.

The pH ranges successfully employed in the present invention are possible because the present invention is t I 6 00 0 Do a 14 4 4o 0a 00 0 0 a a a £R4NT O preferably conducted on fresh carbon-in-pulp (CIP) or carbon-in-leach (CIL) tails. In contrast, previous acidification-volatilization-reneutralization (AVR) processes were employed on decant water or on barren bleed from Merrill-Crowe gold cyanidation processes. In the present process, much of the cyanide in the waste stream is in ionic form or only weakly complexed, whereas in barren bleed there is significant complexing including insoluble and strongly complexed forms. Therefore, previous AVR processes optimized the acidic precipitation of some of the metallo-complexes in order to deal with such precipitates separately. Use of the instant method for treating cyanide-containing slurries has additional advantages when used in combination with a CIL or CIP process. Recyling recovered cyanide and the low levels of effluent cyanide permits higher cyanide levels to be used in the leaching process which provides higher recoveries of precious metal values.

Summary of the Invention In accordance with the present invention, a process is provided for regenerating cyanide from a cyanide-containing mixture. The process includes the steps of: adjusting the pH of the cyanide-containing mixture to between about 6 and about 9.5, volatilizing the hydrogen cyanide (HCN) contained in the pH adjusted mixture, and (3) contacting the volatilized HCN with basic material.

In another embodiment, the instant invention involves a process for regenerating cyanide from alkaline, cyanidecontaining slurry while minimizing equipment fouling due to solids precipitation. The method comprises adjusting the pH of the cyanide-containing slurry to between about 7 and 9.5 to provide a pH adjusted solution; passing a volatilization gas through the pH adjusted slurry to remove HCN from the pH adjusted solution and form an HCN-gas mixture; and contacting the HCN-gas mixture with an bc\14\4511.r2 92 5 13 7 aqueous alkaline solution to form a cyanide salt.

In another embodiment, the instant invention comprises an apparatus for regenerating cyanide values from an alkaline, cyanide-containing slurry. The apparatus comprises a zone for adjusting the pH of the slurry to a pH of between about 6 and about 9.5 to form a pH adjusted slurry. An HCN volatilization zone is adapted to receive the pH adjusted slurry and contact the slurry with a volatilization gas to form an HCN-gas mixture. A cyanide recovery zone is adapted to receive the HCN-gas mixture and contact the mixture with a basic material to form a cyanide "salt.

#0~Q 0 0 In another embodiment the instant invention involves *r an improved method for recovering metal values from an ore.

15 The method involves leaching the ore with a cyanider containing solution at a pH of at least about 10 to provide a cyanide-containing slurry having dissolved metal values.

The cyanide-containing slurry is contacted with activated S0 carbon to load the carbon with the dissolved metal values.

The loaded carbon is separated from the slurry to form a barren slurry having reduced dissolved metal values. The o °pH of the barren slurry is adjusted from above about 10 to between about 6 and about 9.5 to provide a pH adjusted slurry. A volatilization gas is passed through the pH adjusted slurry to form an HCN-gas mixture. The HCN-gas mixture is removed from the pH adjusted slurry and contacted with a basic solution to form a cyanidecontaining solution. The cyanide-containing solution is then returned to the leaching step.

Brief Description of the Drawings Figure 1 is a block diagram of one embodiment of the present invention.

I

i bc\14\4511. r2 92 5 13 I i L~ o *4 000 o 00 00 0 0q 0 0"r 0 0040o Figure 2 illustrates a preferred embodiment of the cyanide recovery process of the present invention.

Figure 3 illustrates a carbon-in-leach process in combination with the cyanide recovery process.

Figure 4 illustrates a carbon-in-pulp process in combination with the cyanide recovery process.

Detailed Description of the Invention The present invention concerns a process for regenerating cyanide from cyanide-containing waste streams. The process is preferably performed on tailings slurries resulting from mineral recovery processes, e.g. gold recovery processes employing cyanide leach solutions, such as vat leach, carbon-inleach, and carbon-in-pulp processes. Such tailings 15 slurries typically have a pH of greater than about contain about 25% to 40% by weight solids and about to 1000, more typically 100 to 600 ppm cyanide.

The recovery of cyanide from slurries is advantageous for a number of reasons. Elimination of sedimentation or clarification steps reduces both capital and operating costs for the process. The recovery of cyanide can significantly reduce operating costs and the hazards associated with the manufacture, transport and storage of the reagent. Reduction of the 25 total and weak acid dissociable (WAD) cyanide content entering the tailings impoundment minimizes the toxic effects of cyanide on wildlife and significantly reduces the potential for generation of leachate containing unacceptable levels of metals and cyanide. The 30 requirement for installing a lining in the tailings impoundment can be eliminated for many applications.

The reduction of total cyanide to acceptable levels in mine backfill can eliminate the need for wash plants in some circumstances. The reduction of total cyanide and metals concentration in the decant water and associated o00 oo So o 0 0 0~ (a 0 0 00 00 0 0 0 L-l- L cyanide waste waters significantly decreases the costs while increasing the reliability and performance of downstream treatment processes. The generation of undesirable treatment byproducts such as ammonia and cyanate can be minimized thereby reducing significant capital outlays required for treatment of such materials. Additionally, the recovery and recycle of a substantial amount of cyanide from mineral recovery streams particularly from vat leaching, CIL and CIP tailings permits higher levels of cyanide to be used in the leach resulting in higher and more rapid recovery of precious metal values.

The cyanide feed streams from minerals recovery processes are typically at a pH above 9 and normally S 15 above 10. A first step in the cyanide recovery process °1 involves adjusting the pH of the stream of the cyanidecontaining mixture being treated to between about 6 and about 9.5, more preferably between about 7 and 9, and most preferably to about 8. This can be accomplished 0 R 20 through the use of an acidifying agent. Using a near neutral or basic pH minimizes problems associated with an increase in sulfate and total dissolved solids concentrations which can result in precipitation of 0 ~materials such as calcium sulfate. Proper adjustment of 0 25 the pH results in the formation of HCN in solution. The HCN is volatilized, preferably by contacting with air.

o *ic The volatilized HCN is then contacted with a basic material, preferably in a solution having a pH between about 11 and 12, to convert the HCN to a cyanide salt.

The tailings remaining after the HCN volatilization step can be further treated to remove remaining cyanide and/or metals and metal complexes. Such optional treatment can include metal coagulation, pH adjustment of the tailings in order to precipitate metal complexes, and/or further cyanide removal by known treatments such -9- Sas oxidation with H 2 0 2 or SO 2 and/or biological treatments.

As a result of the process of the present invention, treated ore tailings have a greater long-term stability. Potentially toxic species silver) will be less likely to be mobilized because of the lower cyanide concentration in the tailings pond. Discharge concentrations can be lowered and management requirements after mine closure reduced.

Previous cyanide recovery processes have used a low pH precipitation step. This is to be contrasted with the present process which instead uses a pH in the range of about 6 to about 9.5. An advantage of using a near neutral or basic pH is that the formation of solids, such as calcium sulfate, is minimized which avoids Sscaling and fouling of equipment. This can be particularly important when packed towers are used to b volatilize the HCN. Another advantage is that the higher pH reduces the amount of acid required to be added to initially acidify the waste stream. The amount of base required to subsequently raise the pH of the treated stream is also reduced.

With reference to Fig. 1, a cyanide-containing r waste stream 12 is treated in a p.i adjustment zone 14 in order to obtain a stream having a pH between about 6 and about 9.5 and more preferably between about 7 and about 4 o9 and most preferably about 8. A cyanide-containing slurry stream from any minerals recovery process can be used as a feed for the instant cyanide recovery process.

In a preferred embodiment, the cyanide-containing waste stream is a tailings slurry from a vat leach which can use a precipitation method such as with zinc to recover metal values, or, a carbon-in-pulp or a carbon-in-leach metal recovery process which tailings normally have a pH above about 10 and normally in the range of about 10.5 to 11.5, a solids content of between about 20% and by weight, more typically 25% to 40% by weight and about 100 600 ppm cyanide. Normally, it is not advantageous to lower the pH of the feed to below about 6. Based upon dissociation constants, more rapid recovery of free cyanide and weakly bound cyanide, e.g., NaCN and Zn(CN) 2 can be accomplished at a pH in the range of 4.5 to 8.5, whereas for a weak acid dissociable (WAD) cyanide, a pH of about 4.0 is optimal. However, it has been found that the instant process provides a high recovery of the ionic cyanide and unexpectedly, a substantial recovery of the WAD cyanide even at a pH of 6 or above. For the reasons set forth hereinabove, a near neutral or basic pH of between about 6 and about more preferably about 7 and about 9, is preferred ao 15 to minimize precipitation problems. Additionally, at pH ranges below about 3 or 4, some metal complexes, e.g.

Cu(CN) 2 will precipitate and subsequently resolubilize 4 when the pH is increased. The dissolution of metals such as iron, copper, nickel, etc. is also minimized o 000 when a pH of at least about 6 is used.

The cyanide-containing stream 12 is acidified in zone 14 by adding an acidifying agent 16. The o0 oacidifying agent 16 is preferably H 2 S0 4 but other 0 44 o0 mineral acids can be used such as hydrochloric acid, nitric acid, phosphoric acid, H 2 S0 3 mixtures of H 2 S0 3 and SO 2 etc. or organic acids such as acetic acid, as well as mixtures of acids. The particular acidifying agent of choice depends on such factors as economics, 4o o particularly the availability of acidic streams from 30 other processes, and the composition of the stream being treated. For example, if the stream contains materials which are detrimentally affected by an oxidizing agent, nitric acid would probably not be useful. A potential problem which was anticipated prior to the reduction to practice of the present invention was the formation of CaSO 4 precipitates upon addition of H 2

SO

4 to slurries -11- !1 !4 r i. containing ore tailings. Surprisingly, this problem was not found to be as severe as originally anticipated and sulfuric acid can be readily used in connection with the packed tower embodiment set forth hereinbelow. The function of the acidifying agent 16 is to reduce the pH in order to shift the equilibrium from cyanide/metal complexes to CN- and ultimately to HCN. By employing higher pH ranges than those used in prior art AVR processes, the amount of acidifying agent 16 required is substantially reduced and the other advantages set forth hereinabove can be obtained.

A pH adjusted stream is then transferred 18 from zone 14 to a volatilization zone 20 as shown in Fig. i.

06In the volatilization zone 20, HCN is transferred from the liquid phase to the gas phase using a volatilization gas 19. Air is a preferred volatilization gas although o other gases such as purified nitrogen can be used. The o gas can also provide the turbulence required. Air can be introduced into the pH adjusted mixture in the volatilization zone 20 by any method well known in the art. For example, a diffuser basin or channel can be used without mechanical dispersion of the air.

o Alternatively, an air sparged vessel and impeller for dispersion can be employed. Baffles can be arranged in the vessel, radially, to assist in agitation of o the slurry. In other alternative embodiments, a modified flotation device or a countercurrent flow tower with a grid, a plurality of grids, packing, a plurality of trays, etc., can be used.

I 30 Volatilization of HCN by gas stripping involves the passage of a large volume of low pressure compressed gas through the acidified mixture to release cyanide from solution in the form of HCN gas. Alternatively, the mixture can be contacted with the volatilization gas, e.g. in a countercurrent flow tower.

-12-

-I

S4 When a stripping reactor is used, the pH adjusted mixture is transferred 18 from the initial pH adjustment zone 14 to the stripping reactor (volatilization zone) Incoming volatilization gas 19 is distributed across the base of the stripping reactor 20 using gas sparger units designed to prevent any solids from entering the gas pipework on cessation of gas flow.

Preferably, coarse to medium sized bubbles are used to provide sufficient gas volume and to minimize clogging of gas ports with materials such as clay. The resulting stripping gas stream is continuously removed 24 from the enclosed atmosphere above the slurry in association with removal of the extracted gas stream 23 which is positively withdrawn from the scrubber zone 26 by a device such as a fan. When the volatilization gas is air, the preferred flow is from about 250 to about 1,000 cubic meters of air per cubic meter of pH adjusted t. -mixture per hour, more preferably, about 300 to 800 and r most preferably, about 350 to about 700 m 3 /m 3 This flow is maintained for a time sufficient to remove the desired level of HCN. The time required to accomplish this removal depends on the air flow rate, the slurry o feed rate, the slurry depth in the stripping reactor, the pH and the temperature of the mixture. Normally, the stripping can be accomplished in a period of about 2 to 6 hours. Preferably, a flow rate of about 300 to 800 o m 3 /m 3 is used which corresponds to a flux of from 2.8 to 7.4 cubic meters air per square meter of pH adjusted mixture per minute, based on a period of 3 to 4 hours.

While the key function of air in the system is to provide an inert carrier gas and transport, the air also has secondary effects. The first is to provide energy to overcome barriers to HCN transfer to the gas phase.

Although HCN is very volatile, having a boiling point of about 26 0 C, it is also infinitely soluble in water, and HCN solutions have a high degree of hydrogen bonding.

-13if *4 o k o ot 0090 o 0 000 0 *0 0 0 00 04 0 o 000 I 040 Thus, there are significant resistances to the mass transfer of HCN that can be overcome by using the sparged air to provide the necessary energy in the form of turbulence. Furthermore, the dissociation equilibrium constants for most of the metal-cyanide complexes are low at the desired pH ranges; therefore, it is necessary for the CN- concentration to be close to zero in order to push the equilibrium far enough toward CN- formation in order to substantially dissociate the complexes. This can be achieved by efficient formation of HCN f rom CN-, which is pH dependent, and then by removal of HON from the solution, which is energy dependent.

As indicated above, preferred retention time in the volatilization zone 20 is from about 2 to about 6 hours with a stripping reactor. In a stripping reactor, the liquid height in the reactor is preferably less than about 3 meters. This preferred depth is due to the function of air in the system and the possibility of 20 bubble coalescence if the depth is greater than about 3 meters. The necessary retention time can be achieved by using a single reactor or a plurality of reactors arranged in parallel, in series or a combination, as is appropriate for the particular feed stream and throughput. For example, multiple trains of reactors can be arranged in parallel with a plurality of stripping reactors arranged in series in each train.

The stream of volatilized HCN and volatilization gas is removed from zone 20 and transferred into a cyanide recovery zone 26. The apparatus useful in the cyanide recovery zone should provide effective mixing of the basic material being added and the stream of volatilized HON. Suitable apparatus includes a gas sparger, preferably in an agitated vessel, which can 35 provide effective contact of the HCN containing gas with the basic solution. More preferably, a conventional -14- 0*00 0 0 0 0* 0 0 0 0 0 oa.

neto 0 *0 0 0 0 *4 0*80*0 0 4 packed countercurrent scrubber is used (126 shown in Fig. Basic material, preferably in solution, is fed 22 to the recovery zone 26. The recovery solution is preferably at a pH of at least about 11 and preferably between about 11 and about 12, in order to absorb HCN gas. Any basic material capable of providing a solution having the desired pH can be used. Examples of such materials include sodium hydroxide, potassium hydroxide, calcium hydroxide, lime, calcium carbonate, sodium carbonate, etc. Calcium-containing materials are generally not preferred because of the potential for the formation of CaSO 4 scale. Sodium hydroxide is generally preferred. The basic cyanide solution 30 can be recycled, e.g. to a mineral recovery process such as a gold cyanidation process.

The treated tailings which remain in reactor after the HCN volatilization step can be removed 28 and contacted in zone 31 with alkaline material 35 to readjust the pH upward to a range of about 9.5 to about 20 10.5 in order to precipitate metals. Generally lime, 44~4 oooo limestone or lime water are preferred basic materials c4due to cost. The resulting pH adjusted tailings 32 can U I then be impounded 34. Optionally, prior to the pH O0adjustment step 31, complexed metals can be coagulated 36 (shown in phantom) by methods known in the art, for example using FeC1 3 or TMT, an organic sulfide available from DeGussa Corporation. Additional cyanide can also removed 33 (shown in phantom) from the pH adjusted tailings 32, for example by known oxidation techniques, 30 e.g. using H 2 0 2 or S02, or by known biological o O44o processes.

A preferred embodiment of the process for removing and recovering cyanide values from a slurry is shown in 4°4 Fig. 2. The pH of an incoming mill tailings slurry 112 is adjusted downward from a pH of above about 10 to between about 6 and about 9.5. This is accomplished in a sealed, agitated reactor vessel 114 normally in approximately a 5 to 20 minute time period. The vessel 114 should be constructed of materials compatible with the abrasive nature of this process. The acidifying agent 116, preferably the H 2

SO

4 shown, is normally added in the form of an aqueous solution normally containing about 10 weight percent acid. Once the pH of the slurry has been adjusted to the range of about 6 to 9.5, the pH adjusted slurry is transferred 118 to the volatilization section 120. Preferably, at least one packed tower is used in which the slurry is passed in countercurrent flow to the volatilization gas.

A packed tower useful in the instant process normally has a means for distributing the slurry substantially uniformly across the top of the packing material. The means is located near the top of the tower and above the packing medium. It is preferred that the distributing means minimize interference between the slurry and rising volatilization gas to 0 minimize the flow disturbance and provide an effective distribution of the slurry over a substantial crosssectional area of the packing material. For example, a multiple weir, V-notch assembly can be used. The distributing means can be made of any suitable material such as steel or ceramic. The tower can also be equipped with a demister. The demister functions to suppress or disperse aerosols and can be formed from a fine screen or grid, glass wool or other porous media, etc.

The packing material useful in the tower can be any mass-transfer media which provides a high void ratio, a high surface area to volume ratio square 1 meter per cubic meter). Preferably, the void ratio is above 50%, more preferably above 80% and most preferably S 35 above 85%. The openings in the packing material must be sufficiently large to allow free passage of the -16particles contained in the slurry. The height of the packing is typically 3 to 10 meters, more preferably 4 to 8 meters, most preferably about 6 to 7 meters depending on the desired pressure drop.

To maximize efficiency of the process, it is important to control the viscosity of the slurry entering the packed tower. It has been found that increasing the viscosity of the slurry within an operative range improves the mass transfer and removal of hydrogen cyanide from the solution. However, if the viscosity is too high, flow of the slurry through the packing can be affected with subsequent operating problems and a decrease in removal of the hydrogen cyanide. The viscosity of the slurry is affected by the percent solids contained in the slurry, the type of ore oO being treated, and the temperature of the slurry.

oo0 Normally, the weight percent solids in the slurry should not exceed about 60 weight percent. Preferably, no more coo than about 50 weight percent solids should be contained 20 in the slurry. More preferably, the slurry should contain between about 25 and 45 weight percent solids.

As set forth hereinabove, the packing material should have a high void ratio. The packing can be any material which can withstand the abrasion and operating conditions in the packed tower. Preferred materials include stainless steel, ceramic materials and plastic materials, for example, polyethylene and polypropylene.

44,4 o0o. Examples of packing materials which have been found to be effective include 50 mm and 75 mm Pall rings, Rashig rings, Tellerette, saddles, and grid, although it is °o anticipated that other packing materials can be used.

The tower can be constructed from any material capable 0 o of withstanding the reaction conditions and the chemicals which contact the internal surface of the tower. The preferred materials include fiberglass, steel (both mild and stainless) and concrete.

-17- -17i i -i ii1 i t i I ii I ii it i -e tI o *11 4 00 O00 4 4 04 66 4 4 4 0400 4 4 44 4r 44 4 4 44 In an alternative configuration, a stripping reactor 122 can be used as discussed for Fig. 1 and as depicted in phantom in Fig. 2. Such a reactor would normally be used in place of the stripping tower 120.

5 In operation of the stripping tower, the volatilization gas, preferably air, is conveyed 119 to the stripping tower 120. Although two towers are depicted in Fig. 2, it is contemplated that, depending on the amount of slurry to be treated and the size of the tower, a single tower could be used. Alternatively, a plurality of stripping towers can be used either in parallel as depicted in Fig. 2 or in series or a combination of parallel trains with each train containing a plurality of towers arranged in series.

The towers can be arranged to provide a single pass of the slurry as depicted in Fig. 2 or multiple passes with the slurry being recycled.

In the operation depicted in Fig. 2, air is introduced into the stripping tower in countercurrent 20 flow to the slurry. The air can be introduced by blower 123 shown in phantom or air can be forced through by negation pressure induced by fan 150. The tower is operated under a negative pressure with the air-HCN mixture being positively removed through line 121 and 25 transported to a cyanide recovery section. In the configuration of Fig. 2, the fan 150 is operated to exceed the flow of stripping gas so that all of the system above the packing in tower 120 through vessel 126 operates under negative pressure to minimize any leaking 30 of HCN. Preferably, the air is recycled as discussed hereinbelow. Sufficient air is introduced into the volatilization tower to provide a mean volume to volume ratio of air to slurry of about 250 to 1,000, more preferably in the range of 300 to 800, and most preferably, in the range of 350 to 700. Preferably, a pressure drop of about 15 millimeters (mm) to about 04 4 4 0 4 4~ 44 4 -18mm water gauge per meter of packing height is maintained. The pressure drop is the difference in pressure between the top and bottom of the tower, the air flow or air flux and the cross-sectional area of the tower. The degree of flooding is based upon filling all of the void space in the tower being considered 100% flooding.

The slurry is fed to the packed tower at a rate which maintains a desired pressure drop over the length of the tower. Normally, the tower is operated in the range of about 10% to about 70% of the flooding volume and preferably, in a range of about 20% to about 50% of the flooding volume.

The air-HCN mixture is conveyed 121 to the cyanide recovery section 126. Preferably, the cyanide recovery takes place in a packed tower by contacting the HCN with a basic solution which is conveyed in countercurrent flow to the HCN-containing gas. As discussed hereinabove for Fig. 1, any appropriate basic material 20 capable of providing an aqueous solution with a pH of at least about 11 can be used. Sodium hydroxide is preferred in order to reduce calcium in the circuit and reduce possible calcium sulfate precipitation and scale formation. Minimizing such scale formation can be particularly important with the packed tower in order to minimize packing media fouling. As depicted in Fig. 2, in a preferred embodiment, sodium hydroxide solution 128 is added to vessel 125 where it is combined with cyanide containing stream 127 from scrubber 126. Caustic stream 129 is removed from vessel 125 by pump 140 and conveyed 141 to be used to scrub hydrogen-cyanide containing gas in the cyanide recovery section 126. The air-HCN mixture is drawn throuegh the scrubber column. As depicted in Fig. 2, the scrubber column is vertical but the column can be horizontal or any other suitable configuration. Additionally, although a single column -19-

I,

0 90 09 *9 o 09 #9 9 o 99@99 op 0 99999 or 9 00 o 0090 0 99 00 0009 9 0 is depicted, it is recognized that a plurality of columns could be used as necessary to effectively scrub the volume of gas. The columns can be arranged in series or in parallel as desired. The column is preferably packed with a media bed to provide efficient contact between the HCN and the basic solution. The media can be any packing capable of providing effective contact between a gas and liquid, with such media being well-known to those skilled in the art. A proportion of the caustic-cyanide solution in vessel 125 bled off 130 to prevent the continuous build-up of cyanide removed from the HCN-air mixture introduced 121. Sodium hydroxide 128 is automatically dosed into the scrubber liquid to maintain a constant pH thereby allowing for the portion lost to bleed. Cyanide, now in the form of a caustic solution of sodium cyanide bleed 130, is returned to the mill circuit for reuse.

Scrubbed air is removed 160 from the scrubber 126 and is conveyed through fan 150 to line 162 for recycle or venting to the atmosphere provided the air contains a low enough level of hydrogen cyanide. Scrubbed air can be discharged to the atmosphere by a line 164. Gas monitoring equipment can be installed in connection with line 162 to provide a continuous readout of p-rformance and can include detection of levels of cyanide.

Preferably, the scrubbing unit 126 allows for a minimum of 98% HCN removal from the hydrogen cyanide-gas mixture. On this basis, the concentration of HCN exiting the scrubber bed is maintained at less than 30 milligrams per cubic meter. Preferably, the scrubbed air is recycled to the volatilization section gas feed 119 through line 166.

The stripped tailings slurry is removed 138 from the volatilization tower and transported to a reneutralization section 131 which is preferably a sealed, agitated vessel. The vessel 131 is constructed

_J

of materials compatible with the abrasive nature of this process. A basic material 135 is added to provide the desired pH level for the final slurry. Although any suitable base such as sodium hydroxide or potassium hydroxide can be used, it is preferred that sodium carbonate, calcium oxide or calcium hydroxide be used to minimize the cost. The normal residence time to accomplish the reneutralization and retain the desired pH level for the slurry is normally about 15 minutes to 1 hour. The necessary time depends upon the buffering curve of the components contained in the slurry.

The adjusted slurry is removed 137 from the reneutralization section and transported to a tailings impoundment. Alternatively, the adjusted tailings can 15 be treated to remove the remaining cyanide or can be *owl transferred to a thickener (not shown) where the coarse S0t material is removed and deposited in an impoundment with the decant being additionally treated to remove the remaining cyanide. The treatment can be accomplished by recycling the whole stream or decant into the feedstream 112 for the pH adjustment section.

Referring to Fig. 3, the use of the instant cyanide recovery process in combination with a carbon-in-leach ao oU process is depicted. Although the CIL process as depicted has no cyanide leach without carbon, it is aea. contemplated that some CIL processes can use at least a or99 partial cyanide leach prior to introduction of the a rc~ carbon. The ore slurry 301 suitable for treatment by a CIL process is prepared by well-known processes 303. An a..

30 oxidation process can be used to treat refractory cres.

The pH of the slurry is adjusted in zone 305 preferably to above about 10, more preferably in the range of about 10.5 to 11 by adding a basic material 307, preferably lime. The resulting alkaline slurry is transferred 309 to the carbon-in-leach process. A typical CIL process is described in United States Patent No. 4,289,532 of -21-

II

Matson et al. (issued 1981) incorporated herein by reference.

In the carbon-in-leach circuit, the slurry is simultaneously contacted with cyanide and granular activated carbon in vessel 311. The carbon moves countercurrent with the flow of the slurry. Thus, in Fig. 3, stream 309 enters the first mixing vessel 311 where it contacts a cyanide stream 313 which can contain cyanide in the amount of between about 0.25 and pounds of cyanide expressed as sodium cyanide per ton of dry ore as disclosed in the Matson et al. '532 patent.

The cyanide can be added in solid form, but it may also be added as a solution, for example, as a sodium cyanide solution having between about 10 and about 25 weight percent sodium cyanide by weight. Other sources of cyanide such as potassium cyanide and calcium cyanide can be used, as is well known in the art. Additional Slime 307 can be added to maintain the pH above about 4 in order to decrease cyanide decomposition. A stream of 4,, the slurry is removed 315 and transferred to a second agitated vessel 317. Activated carbon is screened from the slurry being transferred to vessel 317. Fresh activated carbon is introduced 319 to vessel 317. A slurry containing cyanide ore and activated carbon is transferred 321 back to vessel 311. A slurry containing loaded carbon is removed 323 from vessel 311 for I' 4subsequent recovery of precious metals by methods such as stripping and electro-winning which are well known in the art. A slurry which has been screened to remove the activated carbon is removed 325 from vessel 317 and preferably conveyed to a separation device 327, such as a screen, which removes any contained carbon as stream 329. The remaining ore tailings are transferred 331 as a feed to the instant cyanide recovery process 333 which is depicted in detail in Fig. 2. Sodium cyanide containing solution (depicted as stream 130 in Fig. 2) -22- _I i *00 o 0 0 o ri o o e o aro oo o 0 00o o a 0000 o o0 a 00 o 0 0 o o 0 o 0 0 is removed 335 from the process and recycled to the CIL process. Tailings 337 from the process are disposed of as discussed hereinabove.

Use of the instant cyanide recovery process permits the use of higher levels of cyanide in the CIL process.

The levels of cyanide used based on sodium cyanide can be increased by up to 250%, more typically up to 100%, most typically up to Referring to Fig. 4, a carbon-in-pulp process is depicted using the cyanide recovery process of the present invention. A typical CIP process is described in United States Patent No. 4,578,163 of Kunter et al.

(issued 1986). Ore is prepared in mill 401 and transferred 403 optionally to a classification device 405, such as a cyclone, which classifies the ore into sands and slimes. This classification is used where necessary depending on the ore and whether the sand is to be used as backfill. The sands are conveyed 407 to a vat 409 where the pH of the sand is adjusted to the 20 desired pH range by the use of a basic material 411 such as lime. The vat can be agitated or can be a stationary bed. If a stationary bed of the sand is used, it can be leached using a sodium cyanide solution 413 containing about 0.045 to about 0.055 weight percent sodium cyanide by percolating the solution by gravity through the sand.

If the vat is agitated, then a solution containing about 1 pound of cyanide per ton of ore is used. The sand residue from the process is transferred 415 as a feed to the cyanide recovery 416 process depicted in Fig. 2.

30 The recovered sodium cyanide solution (corresponding to stream 130 of Fig. 2) is recycled 417 to be used as feed for leaching the ore in the vat. The tailings are removed 419 fo- subsequent treatment as discussed hereinabove.

The slime which is separated from the sand by apparatus 405 is transferred 421 to a carbon-in-pulp -23process. Optionally, the ore slurry 403 can be transferred directly from mill 401 to vessel 423 as depicted in phantom. The slime is introduced into the pH adjustment vessel 423 to which a basic material such as lime is added 425 to increase the pH typically to at least about 10 and preferably at least about 10.5. The resulting alkaline slurry is transferred 427 to an agitated vessel 429 to which cyanide 431 is added to provide a final concentration of about 1 pound based on sodium cyanide per ton of slurry. The pulp slurry fed to vessel 429 preferably has a solids content of about weight percent. Pulp from the cyanidation tank 429 is transferred 433 to at least one and normally, a plurality of carbon-in-pulp vessels 435 and 439. As depicted in United States Patent No. 4,578,163 of Kunter et al., normally four or more carbon-in-pulp vessels are operated in series to effect a countercurrent extraction o o 8 with the activated carbon. The activated carbon 437 is 8808 0 fed to the final vessel 439 of the series. A slurry o: 20 containing activated carbon is transferred 441 from 8°O vessel 439 to vessel 435. Simultaneously, a slurry, 0 8 from which the activated carbon has been separated, is o transferred 443 from vessel 435 to vessel 439. Loaded activated carbon is removed 445 from vessel 435 and precious metal values are subsequently removed from the carbon. A slurry stream, from which the activated 0 carbon is substantially removed, is transferred 447 from vessel 439 to a separation means 449 which removes any 4 remaining activated carbon as a stream 451. The 8 30 remaining tailings are transferred 453 to the cyanide recovery process 455 which is depicted in detail in Fig.

2. A sodium cyanide solution (corresponding to stream 130 of Fig. 2) is transferred 457 to be recycled and used in the carbon-in-pulp process. The tailings from process 455 are removed 459 for disposal as discussed hereinabove.

-24- T f

'I

Although two separate cyanide recovery processes are depicted in Fig. 4, a single cyanide recovery process can be used if the different sizes of the particles in the sand slurry and slime slurry permit.

Even if two separate processes are used, sodium cyanide solution can, of course, be recycled to either portion of the process.

Use of the cyanide recovery process of the instant c0 4 4; 4n O-.0 4 0 44,n invention similarly permits higher levels of cyanide to be used particularly in the carbon-in-pulp. The level of cyanide can be readily increased by at least about preferably up to 100% and preferably by at least about 250%.

While not wishing to be bound by any mechanism, it is believed that the cyanide recovery process of the present invention operates as follows.

When the pH of the tailings is adjusted to between 6 and 9.5, the CN- complexes (with the exception of Fe and Co complexes) dissociate to form CN- and ultimately

HCN:

CN complexes CN HCN These equations represent equilibrium reactions in which the process of the present invention shifts the equilibrium to the right-hand side. In the volatilization section 20 of Fig. 1, the HCN in solution is volatilized to HCN gas: HCNsolution HCNgas This preferably occurs under an overall pH of about 8 and a high energy environment of the volatilization section 20. In the basic reaction chamber 26, the high pH causes the equilibrium to shift back towards HCN in solution: HCNgas HCNsolution SAlthough the process has been described with reference to tailings slurry from a carbon-in-leach or carbon-in-pulp mineral recovery process, it is to be rFi expressly understood that the process can also be employed on other cyanide-containing streams, e.g. from other mineral recovery processes, electro-plating processes, etc.

The following experimental results are provided for the purpose of illustration of the present invention and are not intended to limit the scope of the invention.

EXAMPLES

A. Equipment The apparatus employed in Examples 1 and 2 consists of two 3' plexiglass columns six inches in diameter, connected in series, and sealed on both ends with plexiglass plates. The two columns are connected by 88; *tubing to permit the flow of air into the bottom of the 15 first column, up through the column where it exits at 8881 o the top, and then enters the bottom of the second D 0 column, flows through the column and exits at the top of the second column. A flow meter was employed to measure 8881 oa8 the flow of air entering the bottom of the first column.

The column nearest the flow meter operated as the acidification-volatilization column, while the second 0*88 column operated as the absorption column. Tubing was attached to the absorption column and ran into a fume 8 8 hood to vent the air and any cyanide not absorbed.

wt 25 The aeration system was capable of producing a continuous flow of air in the range of 0-10 scfm at o6l pressures of 10-20 psi. A compressor was employed for i this purpose. The compressor was attached to the flow meter via tubing which was then attached to the first column. A regulator between the compressor and the flow meter was employed to regulate and record the pressure being applied to the system.

A pipe was attached in each bottom plate of the two columns to facilitate sampling and draining of the columns during and following an experiment.

-26- B. Procedure In Examples 1, 2 and 3, a specific pH and air flow were utilized and the extent of cyanide stripping and recovery was evaluated over time. The air flow passed from the compressor, through the regulator, the flow meter, and the first volatilization column, and finally through the second absorption column. The air flow exiting the second column passed into a fume hood to vent unabsorbed cyanide.

Example 1 The ore used in Example 1 was prepared by grinding kilograms of ore together with 13.5 kilograms of water 65% solids) and 240 grams of Ca(OH) 2 (i.e.

*o 9.6 kilograms per ton) for 42 minutes in order to 0' 15 achieve a particle size distribution of about 85% of the o ore less than 45 microns in size. Twenty kilograms of water were added after grinding in order to thin the slurry. The slurry was ground a total of 3 times.

off*° Makeup water (9.6 kilograms) was added at the completion of the three grinds and the pH was adjusted to 10.5.

The slurry was leached with cyanide. Initially, *o0: 83.5 grams of NaCN as a 5% solution was added. After 2 S 0 hours, 33 additional grams of NaCN solution) was added as the cyanide concentration had dropped. The total cyanide added to the system was equivalent to 385 parts per million cyanide. During leaching, an air flow Sof 1 liter per minute was maintained. The pH and 0$ cyanide concentration of the leach slurry was monitored hourly. No further additions of NaCN were needed. The 30 final cyanide concentration was measured at 210 parts per million. Finally, carbon was added after 16 hours.

However, the gold and silver concentrations were not monitored. After removal of the carbon, the composition of the barren leachate was measured prior to stripping.

The composition is shown in Table I.

-27- S15 '4* Table I Composition of Barren Leachate Before Stripping pH 10.3 Alkalinity 475 Ammonia-N 1 Cyanate 23 Cyanide (Total) 202, 192 Cyanide (WAD) 200, 190 Sulphate 320 Thiocyanate 24 Arsenic 0.8 Copper 3.90 Iron 0.15 Silver 0.06 Zinc 2.10 0a 4 4 4 4

AG

'49 4 For each of the six runs of Example 1, 10 liters of the slurry prepared as described above were placed in the first volatilization column. Initial samples of the solution were analyzed for free cyanide (for example, by 20 ion selective electrode or by silver nitrate titration), the weak acid dissociable cyanide (CNWAD by ASTM Method and pH. For runs 1 and 2 the initial pH was not adjusted. For runs 3 and 4 the pH was adjusted with

H

2

SO

4 to 8.7. For runs 5 and 6 the pH was adjusted to 25 7.6.

Ten liters of caustic solution was placed in column 2 (the absorption column). The caustic solution was prepared by adding sufficient sodium hydroxide pellets to bring the pH of the solution to about 11 to about 11.5.

Air was then introduced into the columns. In runs 1, 3 and 5, the air flow rate was 60 liters per minute and in runs 2, 4 and 6, the air flow rate was 82 -28- Sliters and air per minute Table II summarizes the pH flow rates for each of the runs in Example 1.

Run No.

pH air flow (1/min) 1 10.5 60 Table II Conditions for Stripping 2 3 4 10.5 8.7 8.7 82 60 82 5 7.6 60 6 7.6 82 o #o B0 4 o o o4* a a e 0 0 0a 0 o0 O 0 04 o o e 0 #0 0 0 0O 4 0 4 0 0 D W e o 4 O 0 The amount of total cyanide (CNT) and Method C cyanide (CNWAD) was measured both in parts per million and in milligrams for the slurry in column 1 and the caustic solution in column 2. The results are shown in Table III.

15 The first column labeled "Hours Stripping" lists the six runs and the time each sample was taken. The second column labeled "Kilograms in System" is the kilograms of liquor in the first column. Initially, kilograms of total slurry was added, made up of liquor 20 and solid tailings. The third and fourth columns list the CNT and CNWAD measurements in parts per million for each run at each time period listed. The fifth and sixth columns list the CNT and CNWAD in milligrams. The seventh and eighth columns list the same measurements as in the sixth and seventh columns except they have been adjusted as to account for the samples which were removed.

Columns 2 through 8 list measurements taken from the slurry in column 1. Columns 9 through 14 list similar measurements which were performed on the caustic solution in column 2 in order to determine the total amount of cyanide absorbed. The percent extraction of CNT and CNWAD are listed in columns 15 and 16.

The percentage extraction of CNT is based on the total CNT figure for that particular hour and includes -29i the adjustments. The extraction percentages are low because the CN drained from the slurry column is i actually not available for stripping. A caustic sample was lost in run number 4 and therefore there are no corresponding numbers. In runs 1 and 2 the milligram SCNWAD analysis was not performed on the slurry.

The 10 liters of initial slurry for runs 3 and 4 required 75 milliliters of a 10 volume percent sulfuric acid solution to reduce the pH to 8.7. For runs 5 and 6, 115 milliliters of a 10 volume percent H 2

SO

4 solution was added to the 10 liters of slurry to reduce the pH to 7.6.

t i 0- 0 o« p p ft Sof 0-30- 0-30 Table III Analyses and Balances of Cyanide

I

L

r, CR SLURRY CAUSTIC

STRIPPING

kg In pp CN D N A MQ CN kg.Fn p00 mg -A3 g- Total CN X E tn system I WAD T AD T W' svsLem CN C CN I w I RUN 1 0 7.91 163 162 129 129 0 10.0 0 0 0 129 1 7.91 258 157 125. 1250 10.0 9.98 100 100 1350 7.4 2 7.68 150 147 115C 1190 9.64 20.3 196 2M 139( 14.4 3 7.50 141 143 106 1120 9.41 29.0 273 281 140 20.1 4 7.20 134 132 96N 1070 9.12 38.1 347 36a 14( 25.5 RUN 2 0 7.87 163 162 128C 1280 10,0 0 0 128 0.9 7.87 157 158 124C 1240 10.0 13.0 130 130 137C 1.8 7.61 141 142 107C 1110 9.35 24.7 236 242 135 517.9 2.7 7,38 136 137 10 1070 9.22 34.0 313 327 1601 23.4 3.6 7.15 114 114 811 920 8.77 41.2 388 7 131C 31.8 RUN 3 0 7.97 16) 162 130C 129C 1 00 1290 10.0 0 0 0 130C 1290 0.9 7.97 50.6 40 40 32 403 319 10.0 91.3 913 913 132C 1230 69.2 74.2 S1.8 7.71 26.6 18.3 20 141 218 151 9.51 109 1040 1080 130C 1230 83.1 87.8 2.7 7.44 20.5 11.7 15 87. 173 102 9.08 116 1050 1140 131 1240 87.0 91.9 3.6 7.17 18.0 8.9 12A 6. E 155 82.3 8.65 120 1040 1180 133 1260 88.7 93.7 BM A 0 7.91 163 162 129 128 1290 1280 10.0 0 0 0 129 1280 10.9 7.91 33.9 27.2 26 21 268 215 10.0 102 1020 1020 129 1240 79.1 82.2 1.8 7.63 18.5 1 .6 141 11 150 127 9.64 112 1080 1120 117C 1250 95.7 89.6 "2.7 7.35 16.3 11.2 12C 82.1 135 94.3 9.28 119 1104 1180 122C 1270 96.7 92.9 3.6 7.04 15.2 9.8 1 0169. 127 86.5 8.88 SAtHE LOST RLN 0 7.54 16) 162 123 122 1230 1220 10.0 0 0 0 123 1220 0.9 7.54 37.2 31,4 28C 23 280 237 10,0 89.3 893 893 117 1130 76.3 79.0 1.8 7.24 22.2 14.0 161 10 172 110 9.55 105 1000 1040 121C 1150 86.0 90.4 2.7 6.93 17.4 10.4 121 72. 139 85.9 9.07 107 970 1060 120r 1150 88,) 92.2 3.6 6.70 13.6 8.9 91 59.1 113 75.8 8.74 101 883 1010 112C 1090 90.2 92.7 N 6 0 7.85 16) 162 128C 127L 1280 1270 10,0 0 0 0 128 1270 0.9 7.85 31.7 23,4 245 181 249 184 10.0 91.8 918 918 117C 1100 78.5 83.5 1. 8 7.55 22.2 11.6 16E 87.4 259 94.6 9.60 112 107$ 1100 1361 1190 80.9 92.4 .7 7.24 16.1 9.9 11 71. 132 82.3 9.14 11J 1040 1150 128e 1230 89.8 9) .C.6 &.92 15.2 8.6 10 5S9 126 73.) 8.77 116 1020 1190 132 1260 90.2 94.4 kg of Muor Adjustments to take Into account withdrawal o cc

P

Sv r -31- Fol1 tests wer air flow run, the compositi Table IV.

t 7~ Example 2 owing the procedure employed in Example 1, new e run on ore samples. In the first run, the was 80 liters per minute In the second air flow was 100 liters per minute The ons before and after the runs are shown in 4*44 4 4 4 44 4 4 44 44 4 O 4* o 0 040* II 4 40 44 4 4 44 40440* 0 -32- Table IV composition of Barren Leachate Before and After Stripping BEFORE

AFTER

Run No. 1 2 Air Flow (1/mm 20%) 80 100 PH 10.4 9.7 10.2 alkalinity 575 170 189 CNT 213 29.4 24.6 C'NWAD 218 7,4 6.8 hardness 307 2170 2030 S0 4 360 2525 2350 *SCN 34 37 38 E.C. (hiS/cm 20 0 C) 1710 As 0.8 0.8 0.

Ca 123 869 814 Cd 0.01 <0.01 0.01 Cr 0.02 0.02 <0.02 Co 0.16 0.33 0.30 Cu 4.7 6.0 6.1 Fe 1.3 8.7 6.7 Pb <0.1 0.1 0.1, Mn 0.01 0.02 0.02 Hg Ni 0,12 0.43 0.41 Ag 0.15 0.04 0.04 Zn 0.64 0.01 0.06 Reagent consumption to either lower or raise pH for 10 1 slurry final pH 8.1 9.7 10.0 reagent 10% v/v H 2 S04 Ca(OH) 2 Ca(0H) 2 amount 110 MI 7.7 g 9.0 g -33i The pH of the initial slurry was 8.1. This pH was achieved by adding 110 milliliters of 10 volume percent

H

2

SO

4 to the 10 liters of slurry. After run number 1, 7.7 grams of Ca(OH) 2 was added to the tails to raise the pH to 9.7. After run number 2, 9.0 grams of Ca(OH) 2 was added to the tails to raise the pH to 10.0. The results for runs number 1 and 2 in Example 2 are shown in Table 0r 0, 44 4e *e 0.~ 4 A g 0i 0 SS 1 -34o 0 C C 0 0 44 00 0 o 0 44 0 0 0 4 4 0 4 0 0 040 0 0 0 0 0 0 0 0 4 0 0 a 00 a 0 0 0 0o~ 000 0 0 *4 0 0 00 o 0 0 00 0 0 0 000 4 0 0 0 9 0 0 a a a 0 0 0 0 S 0 0 0 0 4 Table V Analyses and Balances of Cyanide

T

HOURS

STRIPPING

SLURRY

NaOH kg. in svstem ppm CN r IWAD ~g UN T 1WAO ALJ.Tmq CN kg. in svs tern ppm

CN

AU. mg

CN

Total CN Ex T WAD T system... RUN I 0 1 2 3 4 7.94 7.94 7.66 7.36 7.05 RUN 2 213 41.7 36.3 33.0 25.5 213 37.2 21.

26.0 25.5 23. 5 218 16.7 11.3 10.0 6.0 173C 133 86.6 73.6 42.3 1690 331 290 265 213 1710 298 212 208 194 1730 133 91.3 81.6 53.5 10.0 10.0 9.69 9.32 8.94 0 95.4 95.8 100 98.7 0 954 928 932 882 0 954 957 997 985 169C 129C 125C 126( 120( 1730 1090 1080 1080 1040 74.0 76.6 79.1 82.1

I

tn

WAD

87.5 88.6 92.3 94.7 89.7 95.2 94.3 93.2 0 8.02 1 8.02 2 7.72 3 7.46 4 7.14 218 17.2 8.2 10.2 12.4 175C 138 63.3 76.1 88.5 1750 138 68.4 83.3 99.1 10.0 10.0 9.63 9.28 8.95 0 122 138 133 138 0 1220 1330 1230 1240 0 1220 1380 1320 1380 171C 152C 159( 153C 157C 1750 1360 1450 1400 1480 80.0 86.8 86.3 87.9 kg of liquor S adjustments to take into account withdrawals

I_

i 5 -i 4 o 4 1 i 25 oo 1 t: t Vr Example 3 Five runs were performed in order to test the efficiency of a reactor employing air inlets and a turbine to create turbulence. The pH in each run was varied as was the air flow rate. In run number 1, the pH was 8 and the air flow was 290 liters per minute (2.9 meters 3 /meters 2 x minute). In run number 2, the pH was 7.8 and the air flow rate was 100 liters per minute meters 3 /meters 2 x minute). In run number 3, the pH was 8.2 and the air flow rate was 50 liters per minute meters 3 /meters 2 x minute). In run number 4, the pH was 7.8 and the air flow rate was 200 liters per minute meters 3 /meters 2 x minute). In run number 5, the pH was 8 and the air flow rate was 200 liters per minute. In runs 1 through 5, 30 liters of solution were tested.

Table VI shows the percent CNWAD remaining after 15, 60, 120 and 180 minutes.

Run 1 Table VI 2 3 4 Percent CNWAD Remaining Time (minutes) 60 120 180 59.6 36.5 27.4 22.1 19.2 76.6 58.5 46.3 30.3 23.4 96.8 92.5 46.2 35.5 33.3 52.1 33.3 20.8 12.5 66.2 42.1 24.8 21.1 13.5 4n 4 04( 4 4 4 44 4* 4 4. 44 .4 4-44,4* 4 4 Example 4 The efficiency of a flotation machine and a diffuser column were tested in runs 1 and 2 of Example 4, 30 respectively. In run number 1, a flotation machine was employed with a 40 liter per minute air flow into a 3 liter slurry (1.4 meters 3 /meters 2 x minute). In run number 2, a diffuser column was employed with 50 liters per minute air introduced into a .10 liter slurry (9.4 meters 3 /meters 2 x minute). In both runs 1 and 2, the pH -36was 8. The results of these tests are shown in Table

VII.

Table VII Run 1 2 Time Percent CNWAD Remaining (minutes) 43 76 20 11 46 120 10 12 180 8 7 Example A continuous pilot plant was used in which five stirred vessels sealed to the atmosphere and each having a volume of 200 liters were connected in series with pipes in and out the top of each vessel. The lead o °reactor was connected to a vessel through which tailings 0 slurry could be introduced. The lead reactor was also connected to a vessel from which a 10% solution of sulfuric acid could be added. Arrangement was also made to introduce sodium cyanide as required into the lead reactor in order to maintain a desired level of free cyanide in the slurry being leached. The final reactor in the series was connected to a sealed aeration basin having a coarse bubble flexicap defuser in the bottom region of the basin. The aeration basin was divided with plywood baffles into five sections. Each plywood baffle had a hole in the top with a drop pipe to the j bottom of the next section with the pipe sized to the flow of feed into the basin. Agitation was accomplished by air flow. The diffuser was connected to a source of compressed air with a controller which could provide a range of controlled air flow rates. A transfer line was connected from the top of the sealed aeration basin to a fan which was capable of providing a negative pressure in the aeration basin and conducting the air and -37bb- hydrogen cyanide mixture from the vapor space above the liquid in the aeration basin. The exit of the fan was connected to a dilution stack which diluted the effluent hydrogen cyanide with air to allow venting. Another transfer was connected to the lower portion of the aeration basin to allow removal of tailing slurry and transfer to a stirred sealed neutralization vessel. A transfer line into the vessel was used to introduce sodium hydroxide solution to increase the pH to the desired level or a batch basis as necessry. A transfer line allowed removal of the reneutralized tailings slurry. Results from runs using this procedure are presented in Table VIII and Table IX.

Table VIII o 06 15 Slurry Feed Influent Rate Influent WAD CN- Air Flow Run No. Im3/hr) (pH) (mg/L) m3/m2.min o 0 o 0 0 1 1.7 9.6 230 0 2 1.7 9.6 150 20 3 2.2 9.6 228 4.6 4 2.2 9.7 228 3.9 1.7 9.7 198 4.4 6 1.8 9.7 195 7 2.2 9.8 168 2.4 8 2.2 10.0 182 9 0.5 10.0 207 S' 10 0.5 10.0 157 2.8 ot". 11 0.5 10.0 198 12 0.5 10.0 170 13 0.5 10.0 203 9o, 14 0.5 10.0 179 6.2 0.5 10.0 171 8.8 •16 0.5 9.9 161 17 0.5 9.0 176 o8 000 -38- 1 t

I

Table VIII (continued) Slurry Depth Run No. (Mn) No. of Reactors In Series Total Aeration Period (mn in) Effluent WAD CN- (mg/ L) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 138 138 106 106 138 130 106 92 312 312 312 312 312 312 187 312 312 67 43 67 67 52 84 61 26 28 23 22 23 16 16 19 0 00 0 0 0Q 04~'0 0 0 06, 0 o 44 0 00 00 0 0 0 00 0 0004 0 00 00 0 0 00 *0 0 0 04 00 9 0 00 04. 0 0 00 4 00*000 0 0 Table IX Influent

CN_

Air Flux PH m r 3

M

2 -min Complete mix Reactor Stage Aeration Period (min) Effluent

CN_

198 6.0 4.5 179 8.0 6.2 63 125 187 250 312 63 125 187 249 312 63 125 187 171 8.0 8.8 -39i i

I-~

Example 6 A continuous pilot plant was used as in Example except the agitator was removed from the final pH adjustor reactor in the series and aeration basin was replaced by a packed tower having a diameter of meters and a height of 6 meters. The tower was packed with about 3 meters of either 50 millimeter or millimeter plastic Pall rings. The influent distribution system consisted of a ceramic multiple weir trough and a demister. The packing media was supported by a multiple-beam ceramic gas injector plate. The results from this configuration are provided in Table X for 75 mm rings and Table XI for 50 mm rings.

4" 4 a r'a o d Run No.

1 2 3 4 6 7 8 4 4 4 4 aa 4 4 .4 P* 4O 9 Slurry Flow (i.m3 hr 2.37 2.37 1.94 2.17 2.54 2.10 2.21 2.33 2.39 2.36 2.45 4.1 4.17 Table X Air Flow 3ii/hr) 845 845 839 839 839 2126 2126 1484 1400 1615 1615 2137 2137 2581 2581 No. of Tower Passes 1 1 1 1 1 1 1 1 2 1 2 1 2 1 2 Air/ Liquid Ratio 357 357 432 387 330 1012 962 637 586 684 659 571 534 619 645 Table X (continued) Influent Effluen Run No. WAD CN- WAD CN 1 182 36.6 2 182 24.5 3 156 45.1 4 166.4 22.7 166.4 22.7 t 192.4 192 .4 197. 6 19 .1 223.6 22.0 174. 0 25.0 193 .0 22 .0 15. 0 13.7 18 .3 5.6 23.9 6.0 29.0 26.0 pH of Slurry 7.9 7.9 8.1 7.6 7.7 00 0 0 0 o 0* 0 0900 0 0* 0 0 000 4 00 90 00 0 0 0 0000 0 *000 0000 0 0 0 00 0 0 01 0 4 1 01 0000 000000 0 1 00 0 00 0~000* Run No.

Slurry Flow £flM 3 /hr) 3.9 3.7 4.6 4.0 4.1 4.1 3.9 4 .18 4.2 Table XI Air Flow m364r 1364 1362 1682 2452 2452 1403 1403 243 2389 No. of Tower Passes 1 2 1 2 1 2 1 2 A ir/ Liquid Ratio 349 369 336 365 613 598 342 360 -41-

I

Table XI (continued) Influent Effluent pH of Run No. WAD CN- WAD CN~ Slurry 12 165.0 23.0 7.8 13 186.0 25.0 7.7 14 213.2 17.5 202.8 22.9 7.6 16 170.8 14.4 7.9 17 162.9 14.' While various 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 a 6 15 adaptations are within the spirit and scope of the a0 0 o .o present invention, as set forth in the following claims.

The claims form part of the disclosure of this specification.

0 o4 e a a 0.

0- 0 -42-

Claims (34)

1. A process for regenerating cyanide from a cyanide-containing slurry comprising: adjusting the pH of the cyanide-containing slurry to between about 6 and volatilizing HCN in the pH adjusted slurry from step and contacting the volatilized HCN with a basic material. X..o0 2. The process of claim 1 wherein the pH of the o cyanide-containing slurry is adjusted to between about 7 to 4a 4 Q9. a. a, 9

3. The process of claim 1 wherein the pH of the cyanide-containing slurry is adjusted to about 8. "5 4. The process of claim 1 wherein said cyanide- 9 a containing slurry has a pH of at least about 10 before said pH adjusting and said pH adjusting is accomplished using an acid. 1 5. The process of claim 4 wherein said acid is H 2 SO,.

6. The process of claim 1 wherein the volatilizing of HCN in the pH adjusted slurry is accomplished by introducing air into the pH adjusted slurry or by introducing the pH adjusted slurry into air.

7. The process of claim 1 wherein said basic material is an aqueous solution and said contacting of the volatilized HCN and basic material is accomplished by conducting said HCN and said aqueous solution in a countercurrent flow. bc\13\4511 92 4 23 44

8. The process of claim 7 wherein said basic material is NaOH and said contacting forms NaCN.

9. The process of claim 7 wherein said basic material comprises lime.

10. The process of claim 1 wherein said slurry comprises a tailings slurry resulting from a mineral recovery process employing a cyanide leach.

11. The process of claim 10 wherein said leach is a carbon-in-pulp leach.

12. The process of claim 10 wherein said leach is a a000 *0 carbon-in-leach. a 0 0000^

13. The method of claim 1 wherein said slurry is 0 0 0080 separated from said volatilized HCN and said separated slurry is contacted with a basic material to provide a neutralized slurry.

14. The method of claim 13 wherein liquid and solids are separated from said neutralized slurry and said liquid is treated to remove additional cyanide and said solids are 0o impounded.

15. The method of claim 13 wherein the pH of said neutralized slurry is from about 9.5 to 11.0.

16. The method of claim 8 wherein said NaCN is recycled to provide at least a portion of the cyanide in said cyanide-containing solution.

17. The process of claim 13 further comprising the step of coagulating metal complexes in the neutralized slurry. RA(Z 18. The process of claim 17 wherein said coagulation s bc\13\4511 92 4 23 :I 45 is accomplished by adding FeCl,, an organic sulfide or mixtures thereof.

19. The process of claim 14 wherein said additional cyanide is removed by oxidation.

20. The process of claim 19 wherein H, 2 0 is employed to oxidize said additional cyanide.

21. A process for regenerating cyanide from an alkaline cyanide-containing slurry while minimizing equipment fouling said method comprising: a 0 0 0 adjusting the pH of the cyanide-containing slurry o*4 to between about 7 and 9.5 to provide a pH adjusted nQ t solution; at'" passing a volatilization gas through said pH adjusted slurry to remove HCN from said adjusted solution 5 and form an HCN-gas mixture; and contacting said HCN-gas mixture with a basic solution to form a cyanide salt. S: 22. An apparatus when used for regenerating cyanide from an alkaline, cyanide-containing slurry said apparatus comprising: a zone for adjusting the pH of said slurry to a pH of between about 6 and 9.5 and form a pH adjusted slurry; an HCN volatilization zone adapted to receive said pH adjusted slurry and contact said slurry with a volatilization gas to form a HCN-gas mixture; and a cyanide recovery zone adapted to receive said SHCN-gas mixture and contact said mixture with a basic bc\13\4511 92 5 L2 i 8 I 46 S 4. 44 4 44 material to form a cyanide salt.

23. The apparatus of claim 22 wherein said HCN volatilization zone is at least one packed tower adapted to receive and convey said slurry downward through a packing media while flowing a gas upward through said packing media to form said HCN-gas mixture.

24. The apparatus of claim 23 wherein said packing media has a void ratio of at least about The apparatus of claim 24 wherein said void ratio is at least about

26. The apparatus of claim 25 wherein said cyanide recovery zone is a packed scrubbing tower adapted to convey an alkaline solution having a pH of at least about downward while passing said HCN-gas mixture upward to contact said solution and form a solution containing a cyanide salt.

27. A method for recovering metal values from an ore said method comprising: leaching said ore with a cyanide-containing leaching solution at a pH of at least about 10.0 to provide a cyanide-containing slurry with dissolved metal values; contacting said cyanide-containing slurry with activated carbon to load said carbon with said dissolved metal values; separating said loaded carbon from said slurry to provide a barren slurry; adjusting the pH of said barren slurry from above about 10 to between about 6 and 9.5 to provide a pH T f ~NT O bc\13\4511 92 4 23 P 47 adjusted slurry; passing a volatilization gas through said pH adjusted slurry to form a HCN-gas mixture; removing said HCN-gas mixture from said pH adjusted slurry and contacting said mixture with a basic solution to form a solution containing cyanide; and returning said cyanide solution to said ore leaching.

28. The method of claim 27 wherein said ore is OO'0 simultaneously contacted with said cyanide-containing o a 0 leaching solution and said activated carbon.

29. The method of claim 27 wherein said ore is 0440 a.a: leached with said cyanide-containing leaching E -lution before contacting with said activated carbon.

30. The method of claim 27 wherein said pH adjusted ao slurry and said volatilization gas are contacted in countercurrent flow in a high void ratio media.

31. A process for regenerating cyanide from a a "tailings slurry resulting from a mineral recovery process employing cyanide leach solution, comprising the steps of: adjusting the tailings slurry to a pH of from about pH 6 to pH passing the slurry through a packed tower counter-current to the flow of a volatization gas to volatize HCN; contacting the volatized HCN with a basic material; and ji recovering the basic cyanide solution. bc\13\4511 92 1 23 48

32. A process as claimed in claim 35, wherein the packed tower has a void ratio greater than about percent.

33. A process as claimed in claim 35, wherein said slurry comprises carbon-in-pulp tails.

34. A process as claimed in claim 35, wherein said slurry comprises carbon-in-leach tails. A process as claimed in claim 35, wherein said slurry contains between about 25 and 60 weight percent solids. oo 9 36. A process as recited in claim 35, wherein the packed tower comprises packing media selected from the o 0 group consisting of fiberglass, mild steel, stainless steel, and concrete.

37. The process of claim 1, wherein said volatilizing step comprises contacting the pH adjusted slurry with a volatilizing gas in a packed tower. 0 38. The process of claim 1, wherein said slurry 0 *comprises between about 25 and 60 weight percent solids.

39. The process of claim 21, wherein said passing step occurs in a packed tower. The process of claim 21, wherein said slurry comprises between about 25 and 60 weight percent solids.

41. The method of claim 27, wherein said passing step occurs in a packed tower.

42. The method of claim 27, wherein said slurry comprises between about 25 and 60 weight percent solids.

43. A process for regenerating cyanide substantially bc\13\4511 92 4 23 ng o 44 4 4 0 401 0 44 0 00 a 0 0O 1 o o G a o 49 as hereinbefore described with reference to the accompanying drawings and any one of the Examples.

44. An apparatus for regenerating cyanide substantially as hereinbefore described with reference to the accompanying drawings. A method of recovering metal values substantially as hereinbefore described with reference to the accompanying drawings and Examples. Dated this 23 April, 1992 CARTER SMITH BEADLE Fellows Institute of Patent Attorneys of Australia Patent Attorneys for the Applicant: CYPRUS MINERALS COMPANY 0 00 0* 64 4 a4 a o 4* 0 a 4 a 4 13 bc\13\4511 92 4 23