WO2005100243A1 - Procede d'elimination de thiocyanate d'effluent - Google Patents

Procede d'elimination de thiocyanate d'effluent Download PDF

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Publication number
WO2005100243A1
WO2005100243A1 PCT/AU2005/000543 AU2005000543W WO2005100243A1 WO 2005100243 A1 WO2005100243 A1 WO 2005100243A1 AU 2005000543 W AU2005000543 W AU 2005000543W WO 2005100243 A1 WO2005100243 A1 WO 2005100243A1
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Prior art keywords
thiocyanate
carbon
effluent
ferric
cyanide
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PCT/AU2005/000543
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English (en)
Inventor
Allan Brown
Original Assignee
Suuri Kulta Ab
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Filing date
Publication date
Priority claimed from AU2004901972A external-priority patent/AU2004901972A0/en
Application filed by Suuri Kulta Ab filed Critical Suuri Kulta Ab
Publication of WO2005100243A1 publication Critical patent/WO2005100243A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage

Definitions

  • a PROCESS FOR THE REMOVAL OF THIOCYANATE FROM EFFLUENT FIELD OF THE INVENTION The invention relates to the removal of thiocyanate from effluent, such as that resulting from gold production using cyanide, for instance gold mine tailing slurries, to reduce concentrations of thiocyanate to environmentally acceptable levels. While the invention is particularly applicable to treatment of slurry tailings remaining after precious metal ore extraction, the instant process is equally suitable for treating thiocyanate-containing effluents from other sources including, but without limitation, effluent wash solutions from heap leaching, effluents from electroplating processes and effluents from thiocyanate producing processes.
  • Cyanide is the most effective lixivant for gold and in spite of its toxicity to animal and aquatic life it is probably the most environmentally acceptable.
  • Gold dissolves in cyanide according to the equation Au+2CN “ ⁇ Au(CN)2 " Stoichiometry indicates that 1kg of gold requires 0.497kg of cyanide to dissolve it.
  • Industrial practice shows that the cyanide addition to effectively dissolve gold is 100-500 times the theoretical requirement i.e. a simple 5 gpt non refractory gold ore will often require a cyanide addition of 0.5kg/tonne to achieve a satisfactory gold recovery.
  • Refractory gold ores can be even worse e.g.
  • bacterial oxidation product can assay approximately 125 gpt Au which in theory would only require 62 grams per tonne of sodium cyanide for complete dissolution. The actual requirement can range from 15-30 kgl/tonne or 250-500 times the theoretical requirement. There are a number of reasons for this. a) Cyanide is relatively cheap, USD1.0 per kg compared to gold USD10-12,000.00 per kg so the incentive is to optimize gold recovery not save cyanide. b) Whilst the Au(CN)2 " complex is reasonably stable, the presence of excess cyanide in leach liquor will assist the stability of the complex and thus gold recovery. c) Cyanide reacts with a large number of elements and compounds, this is the major reason for the high cyanide consumption with most ores.
  • Typical reactions would include: CN+S -> SCN xCN+Cu —> Cu(CN)x x 2-4 4CN+Ni ⁇ Ni(CN)4 6CN+C0 -» Co(CN)6 4CN+Zn —» Zn(CN)4 6CN+Fe -> Fe(CN)6
  • the amount of cyanide consumed by cyanicides will be dependent on the quantity of cyanicides present and this can have a major effect on project economics.
  • the reaction of cyanide with sulphur and polysulphides in some products to form thiocyanates can also consume very large amounts of cyanide.
  • NaCN+S ⁇ NaSCN Stoichometry shows that 1 kg of reactive sulphur will consume 1.53 kg of sodium cyanide to form thiocyanates or 1 kg of sodium cyanide will react with sulphur to form 1.65 kg of NaSCN or 1.18 kg of SCN. Whilst the cost of cyanide consumed by either heavy metals or sulphur compounds can be substantial, the major problem occurs when the cyanide and/or thiocyanate in the effluent liquor has to be detoxed prior to discharge. Free cyanide and many cyanide complexes are extremely toxic to animal and aquatic life.
  • the toxic dose of cyanide for a human being is 50-1 OOmg, fish are even more sensitive and some will be affected in water containing as little as 50 micrograms/litre.
  • There are a number of assaying methods for cyanide in solution each method assay not only the free cyanide but also the cyanide complexes.
  • Total cyanide is determined by reducing the pH to 1.0 and assaying the CN by distillation, this technique breaks down all cyanide complexes some of which are non toxic.
  • WAD (weak acid dissociable) cyanide is determined by reducing the pH to 5 and assaying the cyanide by distillation.
  • WAD cyanide Virtually all the complexes assayed as WAD cyanide are toxic so the WAD cyanide assay is the one used when establishing environmental criteria.
  • WAD cyanide is usually defined as: CN ⁇ HCN+Zn and Ni bound CN-fO.75Cu(CN)4+0.67Cu(CN)3+0.5Cu(CN)2 +0.33Ag(CN)3. It should be noted that the above techniques do not assay for thiocyanate or cyanate.
  • WAD cyanide complexes are relatively easy to destroy and there are a number of commercial processes that will reduce the WAD cyanide level of effluent liquors to environmentally acceptable levels including : i) Sulphur Dioxide; ii) Hydrogen Peroxide; iii) Caro's Acid (Peroxymonosulphuric Acid); iv) Alkaline Chlorination; v) Acidification, Volatilization Re-neutralization (AVR) Processes; vi) Biological Degradation; vii) Natural Degradation. Thiocyanates are formed when cyanide reacts with sulphur or sulphur compounds. The thiocyanate level of effluent liquors may vary widely from virtually 0 to 10 000 mg/l.
  • Caro's Acid reacts with thiocyanate forming cyanate and sulphate, further reactions oxidize cyanates to carbonates and ammonia.
  • the quoted Caro's Acid requirement is 4 moles of Caro's Acid per mole of thiocyanate
  • the relevant molecular weights are: SCN - 58 4H 2 S0 5 - 456
  • 7.86 units of Caro's Acid will be required, this assumes of course that the Caro's Acid reacts only with thiocyanate but in fact Caro's Acid is an extremely powerful oxidizing agent and will react with many compounds present in tailings.
  • Caro's Acid is prepared by mixing hydrogen peroxide with sulphuric acid, the approximate cost is USD400 per tonne or USD0.4 per kg.
  • the table below sets out the Caro's Acid requirement and cost to detox liquors containing a range of thiocyanate levels.
  • the invention provides a process for treating effluent containing thiocyanate so as to reduce concentration of the thiocyanate within the effluent, including the steps of: acidifying the effluent to a pH less than 3.0; placing the acidified effluent in the presence of ferric iron; adsorbing and/or absorbing the thiocyanate with activated carbon.
  • ferric iron may be reduced to ferrous and little or no iron may be removed from solution.
  • a study of one embodiment of the invention was carried out and this work (in summary) indicated that, at low pH (circa 2.0) or less and in the presence of ferric iron thiocyanate is converted to the trithiocyanate radical H(SCN) 3 that can be readily absorbed by activated carbon.
  • H(SCN) 3 trithiocyanate radical
  • the ferric iron may be added as ferric sulphate.
  • the invention does not depend on the form of the ferric iron added to the effluent, it is nevertheless important to ensure optimal conditions for the removal of thiocyanate as compared to the addition of a ferrous iron.
  • the removal of thiocyanate in acidic conditions below pH 2 is important.
  • the pH may be equal to or below 1.5.
  • the acidity of the effluent may be reduced using sulphuric acid. As will be shown, the efficiency of the removal of the thiocyanate in an environment above pH2 is considerably reduced.
  • activated carbon whilst activated carbon is an essential feature of the invention, its means of introduction to the effluent may increase the efficiency of adsorption of the thiocyanate.
  • the activated carbon may be introduced in a flow countercurrent to the process stream. Testwork has shown that the adsorption of thiocyanate by activated carbon may be directly related to the solution strength of the slurry and the amount of thiocyanate already adsorbed by the carbon. Thus greater efficiency may be achieved by contacting fresh activated carbon with the low thiocyanate slurry at the end of the process train then contacting the carbon with increasing thiocyanate concentration slurry as the carbon is moved to the head of the process train.
  • hydrogen peroxide may be used to further remove thiocyanate from the treated effluent.
  • testwork has shown that heating the carbon to +400°C in an inert atmosphere removes all the adsorbed compounds and completely reactivates the carbon. Adsorbed tri-thiocyanate has been found to bond more strongly to the carbon than does thiocyanate. Thus, during water-washing of the loaded carbon, the acidic thiocyanate more readily washes off the carbon.
  • Example #1 -Testwork using pure Ferric and Ferrous Ions A series of tests was carried out using pure ferric sulphate, pure ferrous sulphate and sulphuric acid instead of acid ferric liquor to demonstrate that the process was driven by pH and ferric sulphate and not some incidental feed compound in the bacterial oxidation liquor.
  • Example #2 Testwork using pure Sulphuric Acid alone Three tests were carried out to establish the thiocyanate removal by activated carbon in the presence of sulphuric acid with no ferric iron. In each case the GIL tailing was treated with sulphuric acid to reduce the pH to approximately 1.5 before the addition of carbon. The carbon was cycled from one test to the next. The results are shown in Table 2A. These tests show that some removal of thiocyanate is possible in the presence of sulphuric acid without any ferric iron present but the efficiency of removal is significantly reduced. TABLE 2 A
  • Example #3 Removal of Thiocyanate in Non-Acid Conditions
  • 100 g/l of activated carbon removed approximately 1700 mg/l of thiocyanate from a solution containing 10 000 mg/l SCN. This was significantly less than any result in the presence of acid ferric liquor.
  • the carbon sample was not washed with fresh water so the amount of thiocyanate removed with washing was not established. It is concluded that without the acid ferric liquor the efficiency of the thiocyanate removal by activated carbon is very low and thus not a viable commercial process.
  • Example #4 Introduction of Activated Carbon Countercurrent to Effluent Feed
  • activated carbon may absorb up to 20% of its weight of HSCN 3 however the absorption rate may reduce as the carbon becomes loaded. Also, the loading kinetics may increase with increasing thiocyanate concentration in liquor.
  • an effective process may be for the activated carbon to be fed counter current to the GIL tailings treated with acid ferric liquor.
  • a batch counter current test was designed to simulate a continuous process with the activated carbon moving counter currently to the CIL tails. To simulate a continuous process four solutions were used as follows. Solutions 1-3 were from earlier testwork where the thiocyanate had been partially removed. The assays of these solutions were.
  • Solution SCN mg/l 1 1080 2 2890 3 5750 Solution 4 was prepared by adding 150 mls/l of acid ferric liquor to CIL tailings liquor assaying 10 000 mg/l SCN giving a solution containing 8696 mg/l SCN. Carbon was fed sequentially to solutions 1 , 2, 3 and 4 simulating counter current flow. The residence time in each stage was three hours which in a batch test was probably excessive but in a continuous mode would be reasonable residence time to avoid short circuiting etc. Initially four carbon concentrations were used 50, 70, 100 and 140 g/l.
  • a carbon concentration of 70 g/l appears to be slightly in excess of that required to remove 8 696 mg/i of SCN. ⁇
  • the loading kinetics are significantly better in counter current operation than in either batch or concurrent operation.
  • Fresh (or regenerated) carbon is required to remove thiocyanate from low concentration solutions, whilst loaded carbon can remove some thiocyanate from high concentration solutions.
  • the final thiocyanate levels in the tests with 70 g/l carbon were excellent ranging from 23-112 mg/l SCN (the average for five tests was 58 mg/l), at levels less than 100 mg/l SCN the CIL liquor could probably be discharged or if not (the thiocyanate could be) easily removed using bacterial degradation or a small amount of hydrogen peroxide.
  • the testwork demonstrates that the carbon could be regenerated by heating to 600°C and that there is no loss of absorption efficiency after regeneration, in fact regenerated carbon appears to be more efficient.
  • the carbon samples were weighed after each regeneration stage and there was little or no weight loss or gain indicating that there was no build-up of precipitates in the carbon and that carbon losses during regeneration are small.
  • Example #5 Use of Hydrogen Peroxide to Remove Residual Quantities of Thiocyanate
  • a ROLB product solution was prepared from a mix of several products and this was then treated with hydrogen peroxide at three addition rates. As shown in Tables 5A and 5B the removal of thiocyanate using hydrogen peroxide is reasonably consistent.
  • Example #6 Carbon Concentration
  • the cost of carbon regeneration and attrition losses make up the major part of the operating cost of the ROLB process and as such most of the testwork has been directed to optimizing (i.e. minimizing) the carbon requirement.
  • Testwork identified the following: 1.
  • the ultimate thiocyanate adsorbsion capacity of activated carbon is approximately 200 mg per gram, of carbon. This was determined by contacting carbon samples sequentially with acidified high thiocyanate solutions. 2. If a carbon sample is left in contact with the same solution even for a long period the adsorbsion is only 55-65 mg/g. So to achieve optimum loading the carbon must be sequentially contacted with high concentration thiocyanate solutions. 3.
  • Tests 400 and 401 demonstrate the effect of maintaining the pH below 2.0 using acid ferric liquor.
  • the temperature required to regenerate carbon is one in excess of the decomposition temperature of trithiocyanate and related compounds. At this stage for design and future testwork a regeneration temperature of 600°C has been selected, this should be sufficient to remove not only the thiocyanates but also any organic material that may be adsorbed on the carbon.
  • THIOCYANATE ADSORBSION TESTS A series of tests was carried out to establish the adsorbsion kinetics of thiocyanate (trithiocyanate) on activated carbon and also to determine the ultimate loading of thiocyanate (trithiocyanate) on activated carbon.
  • the test procedure was as follows: CIL tailings liquor 10000 mg/l SCN Acid Ferric liquor addition 150 ml/l Initial solution assay 8696 mg/l Carbon additions 100 g/l 100 g/l 75 g/l 50 g/l The carbon was contacted with the solution for a total of 3 hours with samples being taken for assay after 0.5, 1.0, 2.0 and 3.0 hours. The carbon was then removed and recycled to fresh solution without any regeneration. The carbon was used a total of five times (six in the case of the 100 g/l carbon addition). The results of these tests are tabulated and graphed below to show the carbon adsorbsion kinetics.
  • Testwork has shown that if the acid ROLB product is treated with limestone (calcium carbonate) and the pH increased to plus 5.5 in an agitated and aerated environment then the iron is precipitated as a stable carbonate, the aeration oxidising any ferrous to ferric, any base metals are precipitated and arsenic is stabilized in the form of basic ferric arsenate.
  • ICP Inductively coupled plasma
  • the pilot test plant circuit consisted of seven reaction vessels connected in series and included the following: 1 x 15 litre feed mixing reactor 4 x 15 fire ROLB reactors 2 x 30 litre neutralisation reactors
  • a schematic diagram of the circuit is set out below in the attached as Figure 1.
  • the feed to the circuit consisted of equal amounts of carbon in leach (CIL) tailing and acid ferric liquor to give a combined flow rate of 5 litres per hour, the nominal residence time per 15 litre stage was 3 hours.
  • the pH in the feed reactor was maintained at 1.85-1.90 by the controlled addition of 25% (w/w) sulphuric acid.
  • Carbon was added to the four ROLB reactors at a range of concentrations to assess the process efficiency at various carbon concentrations.
  • the carbon was advanced in counter current flow to the flurry at three hourly intervals with the total carbon being advanced to the preceding ROLB reactor. Thus total carbon contact time with the slurry was 12 hours.
  • Fresh or regenerated carbon was added to ROLB Reactor 4 at each carbon advancement.
  • the loaded carbon recovered from ROLB Reactor 1 was lightly washed prior to regeneration in a rotary furnace at 600°C in an inert atmosphere (nitrogen and/or steam) and returned to the circuit at an appropriate stage.
  • the discharge from ROLB Reactor 4 was neutralised in 2 x 30 litre stages where 50% limestone slurry was pumped to Stage 2 at a rate to maintain a pH of 5.5.
  • the subsequent discharge from Stage 2 had a pH of approximately 605.
  • Both neutralisation stages were aerated at a flow rate of approximately 5 litres/min. All stages in the circuit were operated at ambient temperature of approximately 25°C. Monitoring of the process included. • Hourly pH and redox measurement in all reactors. • Three hourly control samples for liquor assays. • Shift composite samples for selected liquor and carbon analysis. • Profile samples taken during steady state conditions.
  • Loaded Carbon Testwork A sample of loaded carbon was regenerated in a rotary furnace in an inert atmosphere under the following conditions. Temperature 600°C. Time 30 minutes. Atmosphere Nitrogen. The off gas was passed sequentially through 1 M NaOH and 1 M H2S04 solutions.
  • WAD cyanide analysis shows that the ROLB process reduced the WAD cyanide concentration from approximately 500mg/l in the feed to approximately 0.26mg/l in final ROLB neutralisation product. This confirmed the determinations carried out in the earlier batch test program.
  • Testwork was carried out on the ROLB product tailings to ensure that they would meet any environmental requirements and to ensure that the products are stable. The following results were obtained.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical & Material Sciences (AREA)
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  • Removal Of Specific Substances (AREA)

Abstract

L'invention concerne un procédé de traitement d'un effluent renfermant du thiocyanate permettant de réduire la concentration du thiocyanate dans l'effluent et comprenant les étapes consistant: à acidifier l'effluent à un pH inférieur à 3,0; à placer l'effluent acidifié en présence de fer ferrique; à adsorber et/ou absorber le thiocyanate au moyen de charbon activé. Le thiocyanate peut être converti en tri-thiocyanate en présence du fer ferrique. Le tri-thiocyanate est ensuite adsorbé et/ou absorbé par le charbon. Le procédé permet de régénérer le charbon à des températures élevées.
PCT/AU2005/000543 2004-04-15 2005-04-15 Procede d'elimination de thiocyanate d'effluent WO2005100243A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2004901972 2004-04-15
AU2004901972A AU2004901972A0 (en) 2004-04-15 A process for the removal of thiocyanate from effluent

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WO2012019243A1 (fr) * 2010-08-13 2012-02-16 The University Of Melbourne Procédé de traitement des solutions aqueuses contenant du thiocyanate
WO2013140299A3 (fr) * 2012-03-20 2013-12-05 Mintails Mining S A (Pty) Limited Traitement de drainage minier acide
US9404168B2 (en) 2013-11-01 2016-08-02 Corem Cyanide-leaching process
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1502477A1 (ru) * 1986-09-25 1989-08-23 Ленинградский Научно-Исследовательский И Проектный Институт Основной Химической Промышленности Способ очистки сточных вод систем мокрой очистки реакционных газов
WO2000035816A1 (fr) * 1998-12-14 2000-06-22 Billiton Sa Limited Biodegradation de thiocyanate et de cyanure
RU2154613C1 (ru) * 1999-06-21 2000-08-20 Байкальский институт природопользования СО РАН Способ очистки сточных вод от цианидов и роданидов

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1502477A1 (ru) * 1986-09-25 1989-08-23 Ленинградский Научно-Исследовательский И Проектный Институт Основной Химической Промышленности Способ очистки сточных вод систем мокрой очистки реакционных газов
WO2000035816A1 (fr) * 1998-12-14 2000-06-22 Billiton Sa Limited Biodegradation de thiocyanate et de cyanure
RU2154613C1 (ru) * 1999-06-21 2000-08-20 Байкальский институт природопользования СО РАН Способ очистки сточных вод от цианидов и роданидов

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 119021, Derwent World Patents Index; AN 1990-162874 *
DATABASE WPI Week 200104, Derwent World Patents Index; AN 2001-030626 *

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102336417B (zh) * 2010-07-21 2014-05-21 苏州久王多铵盐科技有限公司 一种焦炉煤气脱硫脱氰废水中回收硫氰酸钠的方法
CN102336417A (zh) * 2010-07-21 2012-02-01 苏州久王多铵盐科技有限公司 一种焦炉煤气脱硫脱氰废水中回收硫氰酸钠的方法
WO2012019243A1 (fr) * 2010-08-13 2012-02-16 The University Of Melbourne Procédé de traitement des solutions aqueuses contenant du thiocyanate
AU2011288925B2 (en) * 2010-08-13 2013-11-28 The University Of Melbourne Process for treating thiocyanate containing aqueous solutions
US8829061B2 (en) 2010-08-13 2014-09-09 The University Of Melbourne Process for treating thiocyanate containing aqueous solutions
US9120687B2 (en) 2010-08-13 2015-09-01 The University Of Melbourne Polymer inclusion membranes for use in processes for treating thiocyanate containing aqueous solutions
US10928082B2 (en) 2011-09-02 2021-02-23 Nortek Air Solutions Canada, Inc. Energy exchange system for conditioning air in an enclosed structure
US11761645B2 (en) 2011-09-02 2023-09-19 Nortek Air Solutions Canada, Inc. Energy exchange system for conditioning air in an enclosed structure
WO2013140299A3 (fr) * 2012-03-20 2013-12-05 Mintails Mining S A (Pty) Limited Traitement de drainage minier acide
US9487419B2 (en) 2012-03-20 2016-11-08 Mintails Mining S A (Pty) Limited Treatment of acid mine drainage
EA025955B1 (ru) * 2012-03-20 2017-02-28 Минтэйлс Мининг С А (Пти) Лимитед Обработка кислого рудничного дренажа
US11035618B2 (en) 2012-08-24 2021-06-15 Nortek Air Solutions Canada, Inc. Liquid panel assembly
US11732972B2 (en) 2012-08-24 2023-08-22 Nortek Air Solutions Canada, Inc. Liquid panel assembly
US11300364B2 (en) 2013-03-14 2022-04-12 Nortek Air Solutions Canada, Ine. Membrane-integrated energy exchange assembly
US11598534B2 (en) 2013-03-15 2023-03-07 Nortek Air Solutions Canada, Inc. Control system and method for a liquid desiccant air delivery system
US10584884B2 (en) 2013-03-15 2020-03-10 Nortek Air Solutions Canada, Inc. Control system and method for a liquid desiccant air delivery system
CN107300230A (zh) * 2013-03-15 2017-10-27 北狄空气应对加拿大公司 蒸发冷却系统
CN107300230B (zh) * 2013-03-15 2019-11-15 北狄空气应对加拿大公司 蒸发冷却系统
US9404168B2 (en) 2013-11-01 2016-08-02 Corem Cyanide-leaching process
US10712024B2 (en) 2014-08-19 2020-07-14 Nortek Air Solutions Canada, Inc. Liquid to air membrane energy exchangers
CN105906143A (zh) * 2016-05-03 2016-08-31 惠州金茂实业投资有限公司 电镀废水除磷的方法
US11892193B2 (en) 2017-04-18 2024-02-06 Nortek Air Solutions Canada, Inc. Desiccant enhanced evaporative cooling systems and methods
CN109574319A (zh) * 2019-01-07 2019-04-05 紫金矿业集团股份有限公司 有色金属冶炼高砷污酸的固砷工艺
CN109607872A (zh) * 2019-01-07 2019-04-12 紫金矿业集团股份有限公司 一种含砷污酸的综合利用及砷的安全处置方法
CN110496700B (zh) * 2019-07-17 2021-11-26 铜陵有色金属集团股份有限公司 从高砷选金尾矿中回收金的方法及其应用

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