US3739057A - Process for the recovery of rhenium and molybdenum values from molybdenite concentrate - Google Patents

Process for the recovery of rhenium and molybdenum values from molybdenite concentrate Download PDF

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US3739057A
US3739057A US00161111A US3739057DA US3739057A US 3739057 A US3739057 A US 3739057A US 00161111 A US00161111 A US 00161111A US 3739057D A US3739057D A US 3739057DA US 3739057 A US3739057 A US 3739057A
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molybdenum
rhenium
solution
molybdenite
oxidation
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E Daugherty
A Erhard
J Drobnick
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MOLYBDENUM CORP
MOLYBDENUM CORP US
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MOLYBDENUM CORP
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G47/00—Compounds of rhenium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/02—Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • ABSTRACT OF THE DISCLOSURE Process for the recovery of molybdenum and rhenium from molybdenite which comprises: oxidizing the molybdenum in the molybdenite concentrate slurry to the hexavalent form with oxygen or oxygen-containing gases and less than a stoichiometric amount of nitric acid for the sulfide sulfur present, recovering molybdenum and rhenium values from the resulting solution when it contains up to 600 g./l.
  • Rhenium which occurs largely in molybdenite, has now become a valuable metal for use in catalytic applications and others.
  • Prior processes for the recovery of molybdenum from molybdenite have generally not been designed for the recovery of rhenium along with the molybdenum.
  • Substantial recovery of rhenium along with molybdenum would enhance the commercial feasibility of any molybdenum recovery process.
  • a relatively high concentration of nitric acid is required. Further, in order to perform the leaching necessary to recover 99% molybdic oxide as disclosed, it is necessary to at least partially neutralize the sulfuric acid formed in the oxidizing leach.
  • the article also refers to performing the oxidizing leach in two steps.
  • Reduction of the amount of nitric acid used is an important economic consideration. Reduction of nitric acid is a saving in itself and it necessarily results in lesser amounts of nitrogen oxide gases being formed with less oxygen being required to oxidize these gases to prevent their release to the atmosphere and reform nitric acid.
  • Neutralization of the sulfuric acid formed in the oxidizing leach before recovery of dissolved molybdenum is time consuming and the neutralization agent adds to the expense of the process.
  • Neutralization of the sulfuric acid eliminates the possibility of cost reduction through sale of the acid. Further, the presence of contaminant metals or metalloids complicates the recovery of molybdenum by leaching and makes it more difiicult to obtain a high purity product.
  • the principal object of this invention is to provide a process for the recovery in high yields of high purity molybdenum and rhenium from sulfide ores or concentrates by an oxidizing leach process utilizing nitric acid, which requires a minimum amount of nitric acid, eliminates the necessity for neutralizing the sulfuric acid formed during the oxidizing leach, and is effective in the presence of other metal or metalloid contaminants.
  • the process of the invention comprises subjecting finely divided molybdenite concentrate to an oxidizing leach in the presence of nitric acid to form insoluble molybdenum compounds and a solution having dissolved therein the rhenium values and some of the molybdenum values, recovering from the solution the molybdenum and rhenium values with an amine or quaternary ammonium type extractant, stripping molybdenum and rhenium values from the solvent with ammonium hydroxide, separating the rhenium from the molybdenum in the stripping solution with a quaternary ammonium type extractant, followed by final recovery of molybdenum and rhenium by conventional techniques.
  • the process of this invention surprisingly requires about one-tenth the amount of nitric acid required in the prior process.
  • an ion exchange system peculiarly applicable to the molybdenite oxidation leach solution for recovering molybdenum and rhenium values in the solution By the use of an ion exchange system peculiarly applicable to the molybdenite oxidation leach solution for recovering molybdenum and rhenium values in the solution, the necessity of a further molybdenum recovery leaching step is avoided with consequent elimination of the necessity for neutralizing the sulfuric acid formed in the oxidation leach. This leaves the sulfuric acid available for sale.
  • the extraction step recovers rhenium from this oxidation leach solution along with molybdenum. Further, the extraction step selectively recovers molybdenum and rhenium in the presence of the particular contaminant metals and metalloids present in the oxidation leach solution.
  • the process requires about 1025 grams of nitric acid per liter of solution in contrast to the prior process which required about grams per liter.
  • the amount of nitric acid required is about A of the theoretical stoichiometric amount for the reaction involved in the oxidation leach step, i.e.:
  • the particle size of the concentrate As to the particle size of the concentrate, a very small particle size is preferable to provide the maximum feasible contact surface area.
  • the sulfuric acid formed in the process can be marketed without processing the leach solution or it can be readily purified before marketing.
  • the principal contaminant metals are iron and copper.
  • the amine type and quaternary ammonium ion exchange resins used selectively recover molybdenum and rhenium in the presence of these metals.
  • the amine type resins which are operative to extract molybdenum and rhenium values from the oxidation leach solution include conventional long chain primary, secondary and tertiary amines used in the industry as metal ion extractants. Quaternary ammonium compounds may also be used.
  • a preferred amine is a tertiary amine with a mixture of C 43 carbon chains sold under the trade name of Alamine 336.
  • Other preferred amines are those sold under the trade names Amberlite LA-l (secondary amine), Alamine 304 (tri-lauryl amine) and Amberlite XLA-3 (primary amine). These amines are of the type disclosed in US. Pats.
  • amine type resins or amine reagents are referred to herein as amine type resins or amine reagents.
  • the quaternary ammonium extractants are operative for separating rhenium and molybdenum from the alkaline strip solution containing these metals as ammonium molybdate and ammonium perrhenate.
  • quaternary ammonium extractants which are suitable are of the type disclosed in US. Pats. 3,083,085 and 3,575,687.
  • a preferred agent is one being sold under the trade name of Aliquat 336.
  • the amine or quaternary ammonium extractant is highly effective to selectively extract rhenium and molybdenum from the oxidation leach solution which contains metal ion contaminants occurring in molybdenite.
  • the solution also contains sulfates and nitrates among other salts resulting from the catalytic oxidation leach.
  • molybdenum from the molybdenite goes in solution during the oxidation leach step and the remainder is recovered mainly as an insoluble hydrated molybdic oxide, which is calcined to a high purity oxide.
  • the degree of conversion of the molybdenum to the insoluble compound, and consequently the amount to be recovered from solution by the extraction agent, can be controlled.
  • the extraction step, or a second leach step accompanied by neutralization of sulfuric acid as in the prior art, is necessary to recover the molybdenum in solution.
  • the extraction step is necessary to recover the rhenium from the oxidation leach solution. It is an obvious advantage of this invention, resulting in a reduction of required nitric acid, among other advantageous features, that the molybdenum in solution can be recovered in the extraction step necessary for the recovery of rhenium with an extractant peculiarly adaptable for this purpose to the nitric acid treated oxidation leach solution.
  • the oxidizing agent, nitric acid can be supplied as aqueous nitric acid, nitrates, or by the addition of nitrous Oxide gases. whi h a e oxidized to n tr c acid du g the reaction. Oxygen is introduced into the autoclave under pressure as required.
  • the autoclave used was of the conventional type equipped with pressure and temperatureindicating devices.
  • FIG. 1 of the accompanying drawings depicting a flow diagram of the process.
  • the molybdenite concentrate is introduced to the pressure reactor vessel as a wet slurry.
  • Use of the wet slurry is an advantage of the present invention, since in the roasting processes the concentrate used must be dried.
  • water is added as necessary.
  • the slurry may contain as high as 25% solids.
  • Nitric acid is then added to the slurry in the reactor in an amount varying from 0.037 to 0.37 pound of nitric acid per pound of molybdenum in the reactor, depending on the purity of the concentrate employed.
  • the temperature of the slurry containing the nitric acid is raised to about C. prior to introducing oxygen gas to the reactor.
  • Oxygen is introduced to the reactor at varying pressures, a pressure of p.s.i.g. being used in a number of the examples. Oxygen-containing gases may be used.
  • the oxidation leach reaction produces an oxide of nitrogen in which the nitrogen has a lower valence than when introduced to the system, and thus the oxide is volatile and exists in the top of the reactor.
  • the oxygen present will oxidize the nitrogen oxides back to nitric acid and the reaction proceeds as in the beginning.
  • the pressure reactor is then discharged, substantially all of the rhenium being dissolved and at least 85% of the molybdenum values being present as an insoluble hydrated hexavalent molybdenum oxide compound.
  • the solid hexavalent molybdenum oxide can either be dried and marketed or subjected to conventional ammonia dissolution techniques and finally recovered as ammonium molybdate or calcined to produce a high purity molybdenum trioxide.
  • the solution containing the rhenium values and less than 15% of the molybdenum values is subjected to solvent extraction with an amine type or quaternary ammonium solvent to separate the rhenium and molybdenum values from the sulfuric acid and other metal impurities, such as copper, zinc and iron.
  • the molybdenum and rhenium barren sulfuric acid solution can be further processed for recovery of other metal values, such as copper, prior to utilization or discarding to waste.
  • the amine or quaternary ammonium extractant is diluted in either an aliphatic or aromatic hydrocarbon diluent and mixed with the strong sulfuric acid solution resulting from the oxidation leach step, with the result that the molybdenum and rhenium values are transferred to the solvent phase. These metal values are then re-extracted from the solvent phase by mixing with a strip solution containing ammonium hydroxide or other alkaline stripping agent, such as other alkaline hydroxides, carbonates, etc.
  • a strip solution containing ammonium hydroxide or other alkaline stripping agent such as other alkaline hydroxides, carbonates, etc.
  • ammonia strip solution containing ammonium molybdate and ammonium perrhenate is further processed with a quaternary ammonium type extractant or solid ion exchange resin to separate the rhenium from the molybdenum, the rhenium reporting to the solvent phase.
  • a quaternary ammonium type extractant or solid ion exchange resin to separate the rhenium from the molybdenum, the rhenium reporting to the solvent phase.
  • the numeral indicates the wall of the pressure vessel which is provided with cooling jacket 12.
  • the upper body of the vessel 10 terminates in a neck portion 14 terminating in a circular flange 16 defining the top opening of the vessel which is closed by the top 18 secured to flange -16 by bolts and nuts 20.
  • a drain pipe 22 in the bottom of the vessel provided with valve 24 is for draining slurry from the vessel.
  • the vessel is mounted on legs 25.
  • a neck 28 having a flange 30 with a top 32 bolted thereon by bolts and nuts 34 is seated in the top 18 of the vessel.
  • a rotating mechanical seal 36 is mounted in top 32 and a turbine shroud 38 extends into the vessel 10 from the bottom of top 32 and is constructed integral therewith.
  • the shroud is provided with gas inlet orifices 40 on opposite sides.
  • the bottom of the shroud 38 terminates in a flat circular flange 42 which is provided with slurry inlet orifices 44.
  • a motor 46 is mounted on the top 32 for driving turbine shaft 48 to rotate turbine blades 50.
  • a feed inlet pipe 52 provided with valve 54 is mounted in vessel top 18.
  • a pressure gage 56 is also mounted in the top 18 for measuring the internal pressure of the vessel.
  • cooling coils 60 are mounted in the dome section with inlet 62 and outlet 64 extending through the upper wall of the vessel 10. Similar coils 60' are shown schematically in the bottom of the vessel for removing heat from slurry. These coils are optional. They may be mounted with inlet and outlet pipes through the vessel wall-like coils 60
  • a thermowell 68 for liquid temperature and a thermowen 70 for gas phase temperatures are mounted in the vessel wall as shown with the former extending into the slurry area and the latter extending into the gas area.
  • cooling fluid is circulated through the coils and also the coils 60 if the latter are used.
  • Other cooling means to remove heat from the reaction area may be used.
  • EXAMPLE 1 The purpose of this example was to illustrate the conversion of MoS to M00 in a typical nitric acid oxidation of molybdenite.
  • EXAMPLE 2 The purpose of this experiment was to determine the range of nitric acid necessary to dissolve rhenium values in molybdenite and oxidize the quadravalent molybdenum in molybdenite to the hexavalent form.
  • the following solvents were used in this test. All were diluted in an aromatic hydrocarbon having a. flash point of 117 F.
  • EXAMPLE 4 The purpose of this experiment was to determine the effect of oxygen overpressure on oxidation of MoS to M00 over a narrow temperature range. Various oxygen overpressures were used. The temperature varied between 100 to 110 C. The amount of nitric acid used was 0.28 pound per pound of quadravalent molybdenum to be oxidized and the reaction was allowed to proceed for one hour. The results are given in Table 4.
  • EXAMPLE 5 In order to determine the eifect of temperature on molybdenite oxidation, three experiments were performed on 100 gram samples of the concentrate. The nitric acid added to each system was 0.28 pound per pound of quadravalent molybdenum to be oxidized. A pressure of about 150 psi. was used. The reaction period at a given temperature was held constant at one hour. The results are presented in Table 5.
  • EXAMPLE 7 Another extractant was investigated and involved a mixture of 5% Alamine 336 (a mixture of C and C carbon chains having a molecular weight of 392) and 95% Cyclosol 53 (an aromatic hydrocarbon having a flash point of 117 F.), which was mixed with the same solution used in Example 6 to determine the amount of molybdenum which could be extracted. The organic to aqueous phase ratios were varied. The retention time during mixing in separatory funnels was two minutes. The results are reported in Table 7.
  • EXAMPLE 8 This experiment was performed to investigate the range of sulfuric acid concentration within which suitable molybdenum and rhenium extraction can be made.
  • the sulfuric acid concentration of the solution resulting from the oxidation step was adjusted with distilled water or concentrated sulfuric acid. Analysis of the solution indicated that 8.0 g./l. Mo and 0.05 g./l. Re were present in solution.
  • the extractant used for this experiment con- 9 tained 4 volume percent Alamine 304, 5% tridecanol and 91% kerosene.
  • the solvent to aqueous phase ratio was 4 and the phases were mixed for one minute before allowing them to disengage for separation and analysis. The results are reported in Table 8.
  • the secondary amine is marketed by Rohm and Haas Company under the name of Amberlite LA-l, has a molecular weight of 351 to 393 and is mixed with kerosene to result in a solvent containing 10 volume percent Amberlite LA-l.
  • the feed liquor used for this experiment contained 14.58 g./l. Mo and 330 g./1. H 50 Several contacts were made at an organic to aqueous phase ratio of 1. The data is presented in Table 9.
  • a 100-gallon autoclave reactor was charged with 83.0 pounds of molybdenite concentrate containing 67.2 pounds of M00 and 50 gallons of water. The rhenium content was 0.06% (0.0498 pound). The temperature of the slurry was raised to 310 F., and 2.2 pounds of nitric acid were added. Sufficient oxygen was added intermittently to keep the pressure at 140 p.s.i.g. Another 1.1 pounds of nitric acid were added at the end of 20, 40, 60, and 68 minutes of reaction time. Oxygen was fed to the system until the reaction was complete as indicated by the oxygen consumption, which was negligible at the end of 2.0 hours. The temperature measured in the top of the reactor never exceeded 380 F. The slurry was cooled to 200 F. at which time the reactor was discharged. Analysis of the solids and solution indicated that 99.8% of the quadravalent molybdenum had been oxidized to the hexavalent state.
  • the purified strip solution was further contacted with a solvent containing 5% quaternary ammonium compound (Aliquat 336) in 95% Cyclosol 53 diluent to separate the rhenium values from the molybdenum values.
  • a solvent containing 5% quaternary ammonium compound Aliquat 336
  • Cyclosol 53 diluent to separate the rhenium values from the molybdenum values.
  • the rafiinate solution containing the molybdenum values was fed to a spray dryer to recover 15.2 pounds of M00 or 22.6% of the molybdenum introduced to the autoclave reactor.
  • the solvent was stripped of its rhenium values using 1 M perchloric acid to result in a purified rhenium solution containing 97% of the rhenium values or 0.0483 pound of Re in the perchloric acid solution.
  • the rhenium solution was further purified by conventional techniques to produce an ammonium perrhenate product of
  • the solid hydrated molybdenum oxide was leached with an ammonia solution to dissolve the molybdenum values as ammonium molybdate.
  • the ammonia insoluble material was filtered and the ammonium molybdate solution spray dryed to produce a high purity molybdenum trioxide.
  • Ammonium molybdate can be produced, if desired. 50.7 pounds of M00 were recovered during this step of the process, making a total of 65.9 pounds of M00 recovered by the oxidation and solvent extraction steps.
  • the process can be eflectively and economically conducted at temperatures from about 100 C.-200' C. at pressures up to about 300 p.s.i.g. and in a time of not more than about 1-2 hours.
  • the percentage of hexavalent molybdenum which is solubilized in the oxidation leach step can be controlled and it is believed that this percentage has a bearing on the amount of nitric acid used and the overall efliciency of the process. To convert the last 15-20 percent of molybdenum present to the insoluble hydrated molybdic oxide would probably require an unproportionate excess of nitric acid.
  • the invention provides a process by which substantially all of the molybdenum and rhenium values in molybdenite can be recovered in one overall operation. It has the advantage that dissolved rhenium and molybdenum 'values from the oxidation step can be simultaneously recovered in the presence of other metal impurities and large amounts of formed sulfuric acid by the quaternary ammonium or amine type solvent which is peculiarly applicable to the solution resulting from the nitric acid oxidation step. This eliminates the necessity for neutralization of the solvent which was necessary in prior processes for the recovery of dissolved molybdenum with a leaching step.
  • the process has the further advantage that substantially all of the rhenium is dissolved in the oxidation leach step so that it can be recovered along with molybdenum.
  • a process for recovering molybdenum and rhenium values from molybdenite which comprises:
  • a process for the recovery of molybdic oxide and rhendium from molybdenite which comprises:
  • a process for recovering molybdic oxide from molybdenite by oxidation of the molybdenite which comprises:
  • molybdenum solubilized during the oxidation are Usataya, Chemical Abstracts, vol. 47, 1953, p. 5313d.

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860419A (en) * 1971-12-14 1975-01-14 Starck Hermann C Fa Process for the recovery of molybdenum from roasted molybdenum concentrates
US3933971A (en) * 1974-01-28 1976-01-20 E. I. Du Pont De Nemours & Company Molybdenum recovery
JPS5164494A (xx) * 1974-10-17 1976-06-03 Noranda Mines Ltd
US4000244A (en) * 1973-01-30 1976-12-28 Molyscand Ab Wet-chemical digestion of molybdenum sulphide containing material
US4049771A (en) * 1974-09-12 1977-09-20 Gte Sylvania Incorporated Extraction process for recovery of rhenium
US4185078A (en) * 1974-09-12 1980-01-22 Gte Sylvania Incorporated Extraction process for recovery of rhenium
EP0048230A2 (en) * 1980-09-12 1982-03-24 Lumalampan Aktiebolag Procedure for chemical, automatic dissolution of molybdenum core wire in tungsten filament coil and a device for implementing the procedure
ES2211316A1 (es) * 2002-11-15 2004-07-01 Consejo Sup. De Investig. Cientificas. Procedimiento hidrometalurgico para la disolucion y separacion de molibdeno y otros metales de concentrados de molibdenita.
WO2010102391A1 (en) * 2009-03-13 2010-09-16 Recapture Metals Limited Rhenium recovery
US20100263490A1 (en) * 2009-04-16 2010-10-21 Freeport-Mcmoran Copper & Gold Inc. Methods and systems for recovering rhenium from a copper leach
WO2011024164A1 (en) 2009-08-24 2011-03-03 Metal Tech Ltd. Process for multi metal separation from raw materials and system for use
WO2011115660A2 (en) * 2010-03-16 2011-09-22 World Resources Company A method for recovering rhenium and other metals from rhenium-bearing materials
JP2013133233A (ja) * 2011-12-26 2013-07-08 Sumitomo Metal Mining Co Ltd 浸出液の処理方法
CN103361500A (zh) * 2013-07-25 2013-10-23 江西铜业股份有限公司 一种含铼钼焙砂中铼的分离方法
US8753591B2 (en) 2012-03-23 2014-06-17 Kennecott Utah Copper Llc Process for the conversion of molybdenite to molydenum oxide
RU2696989C1 (ru) * 2018-10-15 2019-08-08 Федеральное государственное бюджетное учреждение науки Байкальский институт природопользования Сибирского отделения Российской академии наук (БИП СО РАН) Способ переработки молибденитсодержащих концентратов

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860419A (en) * 1971-12-14 1975-01-14 Starck Hermann C Fa Process for the recovery of molybdenum from roasted molybdenum concentrates
US4000244A (en) * 1973-01-30 1976-12-28 Molyscand Ab Wet-chemical digestion of molybdenum sulphide containing material
US3933971A (en) * 1974-01-28 1976-01-20 E. I. Du Pont De Nemours & Company Molybdenum recovery
US4049771A (en) * 1974-09-12 1977-09-20 Gte Sylvania Incorporated Extraction process for recovery of rhenium
US4185078A (en) * 1974-09-12 1980-01-22 Gte Sylvania Incorporated Extraction process for recovery of rhenium
US3988418A (en) * 1974-10-17 1976-10-26 Noranda Mines Limited Hydrometallurgical production of technical grade molybdic oxide from molybdenite concentrates
JPS5716933B2 (xx) * 1974-10-17 1982-04-08
JPS5164494A (xx) * 1974-10-17 1976-06-03 Noranda Mines Ltd
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DE2232570A1 (de) 1973-01-18
NO141470B (no) 1979-12-10
AT337464B (de) 1977-07-11
BE786010A (fr) 1972-11-03
SE392291B (sv) 1977-03-21
GB1399620A (en) 1975-07-02
AR201264A1 (es) 1975-02-28
IE36545L (en) 1973-01-09
IE36545B1 (en) 1976-11-24
FR2146245B1 (xx) 1978-05-05
IT962536B (it) 1973-12-31
DE2232570B2 (de) 1975-12-11
FR2146245A1 (xx) 1973-03-02
LU65677A1 (xx) 1972-10-30
NL7209095A (xx) 1973-01-11
AU4429272A (en) 1974-01-10
FI55869B (fi) 1979-06-29
FI55869C (fi) 1979-10-10
NO141470C (no) 1980-03-19
ES404686A1 (es) 1975-07-16
ATA578272A (de) 1976-10-15

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