CN104017987B - A kind of method of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore - Google Patents
A kind of method of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore Download PDFInfo
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- CN104017987B CN104017987B CN201410278233.8A CN201410278233A CN104017987B CN 104017987 B CN104017987 B CN 104017987B CN 201410278233 A CN201410278233 A CN 201410278233A CN 104017987 B CN104017987 B CN 104017987B
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Abstract
The invention discloses a kind of method of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore, being included in and being made into particle diameter after adding caking agent, oxygenant and water in rhenium-containing concentrated molybdenum ore is 3 ~ 6mm, moisture is the rhenium-containing concentrated molybdenum ore pelletizing of 8% ~ 12%, then carry out drying, oxidizing roasting and cooling by Concentrate Pellet cloth to the chain grate bed of drying grate, make the molybdenum glance in pelletizing be oxidized to MoO
3, brightness rhenium ore deposit is oxidized to Re
2o
7water wash is adopted to reclaim after volatilization enters flue gas; In above process, the present invention adopts the method for two-stage oxidizing roasting, by different oxidizing roasting temperature and wind speed, improves the oxidation efficiency in molybdenum glance and brightness rhenium ore deposit in Concentrate Pellet, also by being recycled in roasting chamber I by the baking flue gas of roasting chamber II, improve the Re in flue gas
2o
7concentration, and make flue gas maintain 300 ~ 400 DEG C and effectively suppress Re
2o
7by SO
2reduction, thus improve Re
2o
7the rate of recovery; Adopt roasting method of the present invention, evaporation rate>=80% of rhenium in roasting process can be made, content>=90% of solvable molybdenum in molybdenum calcining, the efficient oxidation achieving molybdenum and rhenium be separated.
Description
Technical field
The invention belongs to the molybdenum metallurgy industry in nonferrous metallurgy field, particularly a kind of method of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore.
Background technology
Rhenium is a kind of rare metal granite, and in recent years, its superalloy is growing in the application that Aeronautics and Astronautics is industrial, and demand is also more and more urgent.Only find brightness rhenium ore deposit (ReS so far
2) and copper rhenium sulphide ores (CuReS
4) two kinds of independently rhenium mineral, the most association of rhenium in the mineral such as molybdenum, copper, zinc, lead, and has the rhenium raw material of carrying of utility value to be mainly molybdenum glance MoS
2, wherein can be used for the material of extraction rhenium with brightness rhenium ore deposit ReS
2form exists.Because molybdenum and rhenium are, together with isomorph tax exists, rhenium be carried out purification and utilize, molybdenum first must be made to be separated with rhenium.The treatment process of current rhenium-containing concentrated molybdenum ore is mainly as shown in table 1.
The treatment process contrast of table 1 rhenium-containing concentrated molybdenum ore
In above method, domestic and international minority enterprise adopts lime-roasting method to reclaim molybdenum and rhenium, and this method adds lime in rhenium-containing concentrated molybdenum ore, makes the ReS in rhenium concentrated molybdenum ore by roasting
2and MoS
2be converted into Ca (ReO
4)
2and CaMoO
4, and then make Ca (ReO by aqueous solution leaching
4)
2enter solution, and CaMoO
4water insoluble, reach the object that rhenium molybdenum is separated.Though lime-roasting method is simple, but owing to adding more than 1.5 times that the amount of lime is rhenium-containing Molybdenum Concentrate Grade, cause the content of rhenium and molybdenum more to become dilution, bring processing unit to increase, the problem such as factory building occupation of land increase, extend the enrichment cycle, and cause the rate of recovery of rhenium lower.
Pressure oxidation method is divided into pressure leaching, pressurized acid leaching and alkaline pressure of oxygen leaching three kinds, this method is suitable for processing the many rhenium-containing concentrated molybdenum ores of metal impurities, but needs to arrange oxygen station or add a large amount of strong acid or highly basic oxygenant, and equipment high-quality is expensive, cost remains high, and is difficult to commercial introduction application.
Compare lime-roasting method and pressure oxidation method, oxidizing roasting method (employing atmospheric oxidation) is simple to operate, and does not need additional additive, composes the ReS be stored in concentrated molybdenum ore
2, be easy to be oxidized to high price rhenium oxide Re under concentrated molybdenum ore oxidizing roasting condition
2o
7and volatilization enters flue gas, makes Re by water wash flue gas
2o
7enter liquid phase, then use the method for extraction or ion-exchange by rhenium enrichment, purification.But adopt oxidizing roasting method process rhenium-containing concentrated molybdenum ore still to there are problems at present:
(1) in traditional oxidizing roasting method, to be that particle diameter is less than 200 objects Powdered for concentrated molybdenum ore, and air-flow can not be uniformly distributed in material, and roasting is uneven, is oxidized insufficient, and cause the oxidation ratio of molybdenum, rhenium on the low side, the evaporation rate of rhenium is only about 60%;
(2) roasting process heats up slowly, the Re of generation
2o
7easily be melted into liquid at low temperatures, react with concentrated molybdenum ore and produce molybdate;
(3) in roasting process, particulate concentrated molybdenum ore is easily taken away by flue gas, and not only molybdenum loss amount is large, and dilutes the content of rhenium in flue dust, is unfavorable for the recycling of rhenium;
(4) SO generated in roasting process
2and Re
2o
7together enter flue gas, when flue-gas temperature is lower than 200 DEG C, Re
2o
7easily by SO
2be reduced into the ReO being insoluble in water
2: 2Re
2o
7+ 3SO
2=2ReO
2+ 3SO
3, affect the rate of recovery of rhenium at lessivation.
Therefore, the more efficient roasting method of exploitation one, to improve the oxidation efficiency of rhenium-containing calcining molybdenum ore concentrate process, increases the content of rhenium in flue gas and avoids bringing particulate concentrated molybdenum ore into flue gas, improves baking flue gas temperature to prevent Re simultaneously
2o
7being reduced, is problem demanding prompt solution in the current same industry.
Summary of the invention
Object of the present invention is exactly that there is oxidation insufficient, the oxidation ratio of rhenium, molybdenum is low, and fine grain size concentrated molybdenum ore is easily brought in flue gas for current rhenium-containing concentrated molybdenum ore when adopting oxidizing roasting method to carry out the separation of rhenium molybdenum, and the low Re caused in flue gas of flue-gas temperature
2o
7easily be reduced to the ReO being insoluble in water
2, the problem that rhenium, molybdenum recovery are lower, provides a kind of method of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore.
The method of a kind of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore of the present invention, comprises the following steps:
(1) be 30% ~ 50% in molybdenum grade, rhenium grade is 0.02% ~ 0.1%, with addition of binding agent and oxygenant mixing in the object rhenium-containing concentrated molybdenum ore of particle diameter≤200, after the water adding concentrate quality 0.5% ~ 3.0% again stirs, nodulizer is adopted to be prepared into the rhenium-containing concentrated molybdenum ore pelletizing that particle diameter is 3 ~ 6mm, moisture is 8% ~ 12%; Described binding agent is any one in polyvinyl alcohol or polyacrylamide, and its addition is 0.04% ~ 0.1% of rhenium-containing Molybdenum Concentrate Grade; Described oxygenant is MnO
2, its addition is 1.0% ~ 3.0% of rhenium-containing Molybdenum Concentrate Grade; The principle active component of described rhenium-containing concentrated molybdenum ore is molybdenum glance MoS
2, brightness rhenium ore deposit ReS
2;
(2) by rhenium-containing concentrated molybdenum ore pelletizing cloth on the chain grate bed of drying grate, fabric thickness is 50 ~ 100mm, then rhenium-containing concentrated molybdenum ore pelletizing is made to enter the preheating chamber of drying grate with chain grate bed, temperature be 150 ~ 200 DEG C, dry wind speed dry 20 ~ 30min under being the condition of 1 ~ 2m/s, make moisture≤1% in Concentrate Pellet; Described dry wind be adopt air, distinguished and admirable to material vertical convection;
(3) preheating chamber rhenium-containing concentrated molybdenum ore pelletizing out enters the roasting chamber I of drying grate, temperature be 550 ~ 600 DEG C, oxidation wind speed be the condition of 1.0 ~ 1.8m/s under roasting 1.5 ~ 3h, in the process, the brightness rhenium ore deposit ReS in Concentrate Pellet
2after high temperature oxidation, be converted into Re
2o
7direct distillation enters in flue gas, and flue afterbody is by the Re in elution device water wash recovered flue gas
2o
7after produce rehenic acid ammonium further, the emptying after desulfurization process of the tail gas after drip washing, simultaneously molybdenum glance MoS
2be oxidized into the MoO being soluble in ammoniacal liquor
3stay in pelletizing and become thick molybdenum calcining; Described oxidation wind, from air and the mixed gas through roasting chamber II, requires O in mixed gas
2content>=18%, distinguished and admirable to material vertical convection;
(4) roasting chamber I thick molybdenum calcining out enters the roasting chamber II of drying grate, temperature be 600 ~ 650 DEG C, oxidation wind speed be the condition of 1.2 ~ 2.0m/s under roasting 1 ~ 2h, in the process, rhenium residual in thick molybdenum calcining, further by high temperature oxidation, is converted into Re
2o
7rear volatilization enters in flue gas, namely becomes molybdenum calcining after the roasting of thick molybdenum calcining; Meanwhile, the flue gas recirculation that roasting chamber II produces as the heated air of flue gas in roasting chamber I, makes flue gas remain on 300 ~ 400 DEG C to prevent Re to roasting chamber I
2o
7be reduced, the Re simultaneously in roasting chamber II flue gas
2o
7conflux in the flue gas of roasting chamber I, improve Re
2o
7the rate of recovery; Described oxidation wind be adopt air, distinguished and admirable to material vertical convection;
(5) after roasting completes, molybdenum calcining is put into cooling room, after adopting air molybdenum calcining to be cooled to less than 100 DEG C, refine and reclaim produces ammonium molybdate, and air velocity is 1.5 ~ 2.5m/s; Evaporation rate >=80% of rhenium in the present invention, content >=90% of solvable molybdenum in molybdenum calcining.
Described preheating chamber and roasting chamber I adopt vacuum fan, exhausting below chain grate bed, allow distinguished and admirable to vertically downward with material convection current, adopt gas blower in roasting chamber II, air blast below chain grate bed, allow distinguished and admirable to vertically upward with material convection current, and the flue that is communicated with roasting chamber I is set above roasting chamber II, makes the flue gas recirculation of generation in roasting chamber II in roasting chamber I.
Described nodulizer is balling disc or drum pelletizer.
The advantage of the inventive method is:
(1) rhenium-containing concentrated molybdenum ore is made pelletizing and carry out roasting, oxidation efficiency is higher: by traditional particle diameter≤200 object breeze with addition of caking agent and oxygenant, rhenium-containing concentrated molybdenum ore is prepared into the bead that particle diameter is 3 ~ 6mm, make air-flow when by the bed of material, material fully contacts with oxygen, improve the ventilation property of material in roasting process, the oxygenant MnO simultaneously added
2the oxidation in molybdenum glance and brightness rhenium ore deposit is played to the effect of catalysed promoted, thus improve the oxidation efficiency of rhenium-containing concentrated molybdenum ore, and significantly decrease fine grain size concentrated molybdenum ore and be calcined flue gas and take away;
(2) maturing temperature is changed, by product is avoided to generate: dried rhenium-containing concentrated molybdenum ore pelletizing is directly sent into the higher firing section of temperature, directly distil after ensureing rhenium oxidation and enter flue gas fast, comparing conventional bake method, avoid rhenium-containing concentrated molybdenum ore and generate liquid Re when low-temperature zone roasting
2o
7(fusing point 220 DEG C), easy and concentrated molybdenum ore reacts the difficult problem generating molybdate;
(3) roasting condition is optimized, make oxidation more thorough: according to the feature of molybdenum, rhenium oxidation, reach after 75% at degree of oxidation, oxidation difficulty increases, need higher oxidizing temperature, therefore, the present invention adopts the method for two-stage roasting to carry out oxidizing roasting to rhenium-containing concentrated molybdenum ore, not only ensure that the rhenium in mineral is substantially oxidized, the higher flue gas recirculation of the oxygen level simultaneously produced roasting chamber II is to roasting chamber I, utilize the heat of roasting chamber II flue gas, make the flue gas in roasting chamber I maintain higher temperature, effectively inhibit Re
2o
7by SO
2reduction, improves Re in roasting chamber I flue gas simultaneously
2o
7concentration, thus improve Re in lessivation
2o
7the rate of recovery.
The inventive method is simple, the efficient oxidation that can realize molybdenum, rhenium in rhenium-containing concentrated molybdenum ore be separated, can effectively improve Re in flue gas simultaneously
2o
7the rate of recovery, adopt roasting method of the present invention, evaporation rate>=80% of rhenium in roasting process can be made, content>=90% of solvable molybdenum in molybdenum calcining, enable rhenium-containing concentrated molybdenum ore obtain efficiency utilization.
Accompanying drawing explanation
Fig. 1 is the flow process of material in drying grate and move towards schematic diagram in the present invention.
In figure: 1-rhenium-containing concentrated molybdenum ore pelletizing, 2---drying grate, 3-chain grate bed, 4-preheating chamber, 5-roasting chamber I, 6-roasting chamber II, 7-elution device, 8-vacuum fan, 9-gas blower, 10-flue.
Embodiment
Explain the present invention in detail below by embodiment and accompanying drawing 1, but following embodiment does not limit the present invention in any way.
Embodiment 1
(1) be 40% in molybdenum grade, rhenium grade is 0.034%, with addition of binding agent and oxygenant mixing in the object rhenium-containing concentrated molybdenum ore of particle diameter≤200, then after the water adding concentrate quality 3.0% stirs, balling disc is adopted to be prepared into the rhenium-containing concentrated molybdenum ore pelletizing 1 that particle diameter is 3mm, moisture is 12%; Described binding agent is any one in polyvinyl alcohol or polyacrylamide, and its addition is 0.04% of rhenium-containing Molybdenum Concentrate Grade; Described oxygenant is MnO
2, its addition is 3.0% of rhenium-containing Molybdenum Concentrate Grade, and the principle active component of described rhenium-containing concentrated molybdenum ore is molybdenum glance MoS
2, brightness rhenium ore deposit ReS
2;
(2) by rhenium-containing concentrated molybdenum ore pelletizing cloth on the chain grate bed 3 of drying grate 2, fabric thickness is 50mm, then rhenium-containing concentrated molybdenum ore pelletizing is made to enter the preheating chamber 4 of drying grate with chain grate bed, temperature be 150 DEG C, dry wind speed be 2.0m/s hot blast condition under dry 30min, make moisture≤1% in Concentrate Pellet; Described dry wind be adopt air, distinguished and admirable to material vertical convection;
(3) preheating chamber 4 rhenium-containing concentrated molybdenum ore pelletizing out enters the roasting chamber I 5 of drying grate, temperature be 550 DEG C, oxidation wind speed be the condition of 1.0m/s under roasting 3h, in the process, the brightness rhenium ore deposit ReS in Concentrate Pellet
2after high temperature oxidation, be converted into Re
2o
7direct distillation enters in flue gas, and flue afterbody is by the Re in elution device 7 water wash recovered flue gas
2o
7after produce rehenic acid ammonium further, the emptying after desulfurization process of the tail gas after drip washing, simultaneously molybdenum glance MoS
2be oxidized into the MoO being soluble in ammoniacal liquor
3stay in pelletizing and become thick molybdenum calcining; Described oxidation wind, from air and the mixed gas through roasting chamber II 6, requires O in mixed gas
2content>=18%, distinguished and admirable to material vertical convection;
(4) roasting chamber I 5 thick molybdenum calcining out enters the roasting chamber II 6 of drying grate, temperature be 600 DEG C, oxidation wind speed be the condition of 1.2m/s under roasting 2h, in above process, rhenium residual in thick molybdenum calcining, further by high temperature oxidation, is converted into Re
2o
7rear volatilization enters in flue gas, namely becomes molybdenum calcining after the roasting of thick molybdenum calcining; Meanwhile, the flue gas recirculation that roasting chamber II produces as the heated air of flue gas in roasting chamber I, makes flue gas remain on 300 DEG C to prevent Re to roasting chamber I
2o
7be reduced, the Re simultaneously in roasting chamber II flue gas
2o
7conflux in the flue gas of roasting chamber I, improve Re
2o
7the rate of recovery; Described oxidation wind be adopt air, distinguished and admirable to material vertical convection;
(5) after roasting completes, molybdenum calcining is put into cooling room, after adopting air molybdenum calcining to be cooled to less than 100 DEG C, refine and reclaim produces ammonium molybdate, and air velocity is 1.5m/s; In the present embodiment, the evaporation rate of rhenium is 81%, and in molybdenum calcining, the content of solvable molybdenum is 90%.
Described preheating chamber 4 and roasting chamber I 5 adopt vacuum fan 8, exhausting below chain grate bed 3, allow distinguished and admirable to vertically downward with material convection current, adopt gas blower 9 in roasting chamber II 6, air blast below chain grate bed, allow distinguished and admirable to vertically upward with material convection current, and the flue 10 that is communicated with roasting chamber I is set above roasting chamber II, makes the flue gas recirculation of generation in roasting chamber II in roasting chamber I.
Embodiment 2
(1) be 30% in molybdenum grade, rhenium grade is 0.02%, with addition of binding agent and oxygenant mixing in the object rhenium-containing concentrated molybdenum ore of particle diameter≤200, then after the water adding concentrate quality 2.0% stirs, drum pelletizer is adopted to be prepared into the rhenium-containing concentrated molybdenum ore pelletizing that particle diameter is 4mm, moisture is 10%; Described binding agent is any one in polyvinyl alcohol or polyacrylamide, and its addition is 0.06% of rhenium-containing Molybdenum Concentrate Grade; Described oxygenant is MnO
2, its addition is 2.0% of rhenium-containing Molybdenum Concentrate Grade;
(2) by rhenium-containing concentrated molybdenum ore pelletizing cloth on the chain grate bed of drying grate, fabric thickness is 60mm, then make rhenium-containing concentrated molybdenum ore pelletizing enter the preheating chamber of drying grate with chain grate bed, temperature be 185 DEG C, dry wind speed be the condition of 1.5m/s under dry 25min, make moisture≤1% in Concentrate Pellet; Described dry wind be adopt air, distinguished and admirable to material vertical convection;
(3) preheating chamber rhenium-containing concentrated molybdenum ore pelletizing out enters the roasting chamber I of drying grate, temperature be 570 DEG C, oxidation wind speed be the condition of 1.2m/s under roasting 2h, in the process, the brightness rhenium ore deposit ReS in Concentrate Pellet
2after high temperature oxidation, be converted into Re
2o
7direct distillation enters in flue gas, and flue afterbody is by the Re in elution device water wash recovered flue gas
2o
7after produce rehenic acid ammonium further, the emptying after desulfurization process of the tail gas after drip washing, simultaneously molybdenum glance MoS
2be oxidized into the MoO being soluble in ammoniacal liquor
3stay in pelletizing and become thick molybdenum calcining; Described oxidation wind, from air and the mixed gas through roasting chamber II, requires O in mixed gas
2content>=21%, distinguished and admirable to material vertical convection;
(4) roasting chamber I thick molybdenum calcining out enters the roasting chamber II of drying grate, temperature be 630 DEG C, oxidation wind speed be the condition of 1.6m/s under roasting 1.5h, in above process, rhenium residual in thick molybdenum calcining, further by high temperature oxidation, is converted into Re
2o
7rear volatilization enters in flue gas, namely becomes molybdenum calcining after the roasting of thick molybdenum calcining; Meanwhile, the flue gas recirculation that roasting chamber II produces as the heated air of flue gas in roasting chamber I, makes flue gas remain on 350 DEG C to prevent Re to roasting chamber I
2o
7be reduced, the Re simultaneously in roasting chamber II flue gas
2o
7conflux in the flue gas of roasting chamber I, improve Re
2o
7the rate of recovery; Described oxidation wind be adopt air, distinguished and admirable to material vertical convection;
(5) after roasting completes, molybdenum calcining is put into cooling room, after adopting air molybdenum calcining to be cooled to less than 100 DEG C, refine and reclaim produces ammonium molybdate, and air velocity is 2.0m/s; In the present embodiment, the evaporation rate of rhenium is 80%, and in molybdenum calcining, the content of solvable molybdenum is 90%.
Described preheating chamber and roasting chamber I adopt vacuum fan, exhausting below chain grate bed, allow distinguished and admirable to vertically downward with material convection current, adopt gas blower in roasting chamber II, air blast below chain grate bed, allow distinguished and admirable to vertically upward with material convection current, and the flue that is communicated with roasting chamber I is set above roasting chamber II, makes the flue gas recirculation of generation in roasting chamber II in roasting chamber I.
Embodiment 3
(1) be 50% in molybdenum grade, rhenium grade is 0.1%, with addition of binding agent and oxygenant mixing in the object rhenium-containing concentrated molybdenum ore of particle diameter≤200, then after the water adding concentrate quality 2.5% stirs, balling disc is adopted to be prepared into the rhenium-containing concentrated molybdenum ore pelletizing that particle diameter is 5mm, moisture is 11%; Described binding agent is any one in polyvinyl alcohol or polyacrylamide, and its addition is 0.08% of rhenium-containing Molybdenum Concentrate Grade; Described oxygenant is MnO
2, its addition is 2.5% of rhenium-containing Molybdenum Concentrate Grade, and the principle active component of described rhenium-containing concentrated molybdenum ore is molybdenum glance MoS
2, brightness rhenium ore deposit ReS
2;
(2) by rhenium-containing concentrated molybdenum ore pelletizing cloth on the chain grate bed of drying grate, fabric thickness is 80mm, then rhenium-containing concentrated molybdenum ore pelletizing is made to enter the preheating chamber of drying grate with chain grate bed, temperature be 175 DEG C, dry wind speed be 1.8m/s hot blast condition under dry 22min, make moisture≤1% in Concentrate Pellet; Described dry wind be adopt air, distinguished and admirable to material vertical convection;
(3) preheating chamber rhenium-containing concentrated molybdenum ore pelletizing out enters the roasting chamber I of drying grate, temperature be 590 DEG C, oxidation wind speed be the condition of 1.5m/s under roasting 2.5h, in the process, the brightness rhenium ore deposit ReS in Concentrate Pellet
2after high temperature oxidation, be converted into Re
2o
7direct distillation enters in flue gas, and flue afterbody is by the Re in elution device water wash recovered flue gas
2o
7after produce rehenic acid ammonium further, the emptying after desulfurization process of the tail gas after drip washing, simultaneously molybdenum glance MoS
2be oxidized into the MoO being soluble in ammoniacal liquor
3stay in pelletizing and become thick molybdenum calcining; Described oxidation wind, from the mixed gas of air and process, requires O in mixed gas
2content>=20%, distinguished and admirable to material vertical convection;
(4) roasting chamber I thick molybdenum calcining out enters the roasting chamber II of drying grate, temperature be 620 DEG C, oxidation wind speed be the condition of 1.8m/s under roasting 1.7h, in above process, rhenium residual in thick molybdenum calcining, further by high temperature oxidation, is converted into Re
2o
7rear volatilization enters in flue gas, namely becomes molybdenum calcining after the roasting of thick molybdenum calcining; Meanwhile, the flue gas recirculation that roasting chamber II produces as the heated air of flue gas in roasting chamber I, makes flue gas remain on 370 DEG C to prevent Re to roasting chamber I
2o
7be reduced, the Re simultaneously in roasting chamber II flue gas
2o
7conflux in the flue gas of roasting chamber I, improve Re
2o
7the rate of recovery; Described oxidation wind be adopt air, distinguished and admirable to material vertical convection;
(5) after roasting completes, molybdenum calcining is put into cooling room, after adopting air molybdenum calcining to be cooled to less than 100 DEG C, refine and reclaim produces ammonium molybdate, and air velocity is 2.2m/s; In the present embodiment, the evaporation rate of rhenium is 85%, and in molybdenum calcining, the content of solvable molybdenum is 94%.
Described preheating chamber and roasting chamber I adopt vacuum fan, exhausting below chain grate bed, allow distinguished and admirable to vertically downward with material convection current, adopt gas blower in roasting chamber II, air blast below chain grate bed, allow distinguished and admirable to vertically upward with material convection current, and the flue that is communicated with roasting chamber I is set above roasting chamber II, makes the flue gas recirculation of generation in roasting chamber II in roasting chamber I.
Embodiment 4
(1) be 44% in molybdenum grade, rhenium grade is 0.042%, with addition of binding agent and oxygenant mixing in the object rhenium-containing concentrated molybdenum ore of particle diameter≤200, then after the water adding concentrate quality 0.5% stirs, balling disc is adopted to be prepared into the rhenium-containing concentrated molybdenum ore pelletizing that particle diameter is 6mm, moisture is 8%; Described binding agent is any one in polyvinyl alcohol or polyacrylamide, and its addition is 0.1% of rhenium-containing Molybdenum Concentrate Grade; Described oxygenant is MnO
2, its addition is 1.0% of rhenium-containing Molybdenum Concentrate Grade, and the principle active component of described rhenium-containing concentrated molybdenum ore is molybdenum glance MoS
2, brightness rhenium ore deposit ReS
2;
(2) by rhenium-containing concentrated molybdenum ore pelletizing cloth on the chain grate bed of drying grate, fabric thickness is 100mm, then rhenium-containing concentrated molybdenum ore pelletizing is made to enter the preheating chamber of drying grate with chain grate bed, temperature be 200 DEG C, dry wind speed be 1m/s hot blast condition under dry 20min, make moisture≤1% in Concentrate Pellet; Described dry wind be adopt air, distinguished and admirable to material vertical convection;
(3) preheating chamber rhenium-containing concentrated molybdenum ore pelletizing out enters the roasting chamber I of drying grate, temperature be 600 DEG C, oxidation wind speed be the condition of 1.8m/s under roasting 1.5h, in the process, the brightness rhenium ore deposit ReS in Concentrate Pellet
2after high temperature oxidation, be converted into Re
2o
7direct distillation enters in flue gas, and flue afterbody is by the Re in elution device water wash recovered flue gas
2o
7after produce rehenic acid ammonium further, the emptying after desulfurization process of the tail gas after drip washing, simultaneously molybdenum glance MoS
2be oxidized into the MoO being soluble in ammoniacal liquor
3stay in pelletizing and become thick molybdenum calcining; Described oxidation wind, from air and the mixed gas through roasting chamber II, requires O in mixed gas
2content>=19%, distinguished and admirable to material vertical convection;
(4) roasting chamber I thick molybdenum calcining out enters the roasting chamber II of drying grate, temperature be 650 DEG C, oxidation wind speed be the condition of 2.0m/s under roasting 1h, in above process, rhenium residual in thick molybdenum calcining, further by high temperature oxidation, is converted into Re
2o
7rear volatilization enters in flue gas, namely becomes molybdenum calcining after the roasting of thick molybdenum calcining; Meanwhile, the flue gas recirculation that roasting chamber II produces as the heated air of flue gas in roasting chamber I, makes flue gas remain on 400 DEG C to prevent Re to roasting chamber I
2o
7be reduced, the Re simultaneously in roasting chamber II flue gas
2o
7conflux in the flue gas of roasting chamber I, improve Re
2o
7the rate of recovery; Described oxidation wind be adopt air, distinguished and admirable to material vertical convection;
(5) after roasting completes, molybdenum calcining is put into cooling room, after adopting air molybdenum calcining to be cooled to less than 100 DEG C, refine and reclaim produces ammonium molybdate, and air velocity is 2.5m/s; In the present embodiment, the evaporation rate of rhenium is 83%, and in molybdenum calcining, the content of solvable molybdenum is 93%.
Described preheating chamber and roasting chamber I adopt vacuum fan, exhausting below chain grate bed, allow distinguished and admirable to vertically downward with material convection current, adopt gas blower in roasting chamber II, air blast below chain grate bed, allow distinguished and admirable to vertically upward with material convection current, and the flue that is communicated with roasting chamber I is set above roasting chamber II, makes the flue gas recirculation of generation in roasting chamber II in roasting chamber I.
The flow direction of above-described embodiment apoplexy also can change, as long as with material vertical convection, and by the flue gas recirculation in roasting chamber II in roasting chamber I.
Claims (4)
1. the method for Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore, is characterized in that comprising the following steps:
(1) be 30% ~ 50% in molybdenum grade, rhenium grade is 0.02% ~ 0.1%, with addition of binding agent and oxygenant mixing in the object rhenium-containing concentrated molybdenum ore of particle diameter≤200, after the water adding concentrate quality 0.5% ~ 3.0% again stirs, nodulizer is adopted to be prepared into the rhenium-containing concentrated molybdenum ore pelletizing that particle diameter is 3 ~ 6mm, moisture is 8% ~ 12%; Described binding agent is any one in polyvinyl alcohol or polyacrylamide, and its addition is 0.04% ~ 0.1% of rhenium-containing Molybdenum Concentrate Grade; Described oxygenant is MnO
2, its addition is 1.0% ~ 3.0% of rhenium-containing Molybdenum Concentrate Grade;
(2) by rhenium-containing concentrated molybdenum ore pelletizing cloth on the chain grate bed of drying grate, fabric thickness is 50 ~ 100mm, then rhenium-containing concentrated molybdenum ore pelletizing is made to enter the preheating chamber of drying grate with chain grate bed, temperature be 150 ~ 200 DEG C, dry wind speed dry 20 ~ 30min under being the condition of 1 ~ 2m/s, make moisture≤1% in Concentrate Pellet; Described dry wind be adopt air, distinguished and admirable to material vertical convection;
(3) preheating chamber rhenium-containing concentrated molybdenum ore pelletizing out enters the roasting chamber I of drying grate, temperature be 550 ~ 600 DEG C, oxidation wind speed be the condition of 1.0 ~ 1.8m/s under roasting 1.5 ~ 3h, in the process, the brightness rhenium ore deposit in Concentrate Pellet is converted into Re
2o
7direct distillation enters in flue gas, and flue afterbody reclaims Re by elution device
2o
7after produce rehenic acid ammonium further, simultaneously molybdenum glance is oxidized into the MoO being soluble in ammoniacal liquor
3stay in pelletizing and become thick molybdenum calcining; Described oxidation wind, from air and the mixed gas through roasting chamber II, requires O in mixed gas
2content>=18%, distinguished and admirable to material vertical convection;
(4) roasting chamber I thick molybdenum calcining out enters the roasting chamber II of drying grate, temperature be 600 ~ 650 DEG C, oxidation wind speed be the condition of 1.2 ~ 2.0m/s under roasting 1 ~ 2h, in the process, rhenium residual in thick molybdenum calcining is converted into Re
2o
7rear volatilization enters in flue gas, namely becomes molybdenum calcining after the roasting of thick molybdenum calcining completes; Meanwhile, roasting chamber II produce flue gas recirculation to roasting chamber I as the heated air of flue gas in roasting chamber I; Described oxidation wind be adopt air, distinguished and admirable to material vertical convection;
(5) after roasting completes, molybdenum calcining is put into cooling room, after adopting air molybdenum calcining to be cooled to less than 100 DEG C, refine and reclaim produces ammonium molybdate, and air velocity is 1.5 ~ 2.5m/s; Evaporation rate >=80% of rhenium in the method, content >=90% of solvable molybdenum in molybdenum calcining.
2. the method for a kind of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore according to claim 1, it is characterized in that: described preheating chamber and roasting chamber I adopt vacuum fan, exhausting below chain grate bed, allow distinguished and admirable to vertically downward with material convection current, in roasting chamber II be adopt gas blower, air blast below chain grate bed, allow distinguished and admirable to vertically upward with material convection current, and the flue be communicated with roasting chamber I is set above roasting chamber II, make the flue gas recirculation produced in roasting chamber II in roasting chamber I.
3. the method for a kind of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore according to claim 1, is characterized in that: described nodulizer is balling disc or drum pelletizer.
4. the method for a kind of Separation of Molybdenum and rhenium from rhenium-containing concentrated molybdenum ore according to claim 1, is characterized in that: from roasting chamber I, flue gas out reclaims Re through drip washing
2o
7the tail gas of rear generation carries out desulfurization process emptying.
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| CN104630509B (en) * | 2015-02-03 | 2016-11-23 | 嵩县开拓者钼业有限公司 | A kind of method preparing ammonium perrhenate |
| CN105112647B (en) * | 2015-09-06 | 2017-12-05 | 中南大学 | A kind of solid sulphur method of Low Grade Molybdenum Concentrates lime method roasting |
| CN108193060B (en) * | 2018-01-04 | 2019-08-23 | 中南大学 | Rhenium-containing molybdenum concentrate volatilization-water logging separation molybdenum-rhenium method |
| CN109675405A (en) * | 2019-03-11 | 2019-04-26 | 杨松 | A kind of cooling activation chain conveyer grate operation method of VOCs waste-gas adsorbant |
| CN109852812B (en) * | 2019-04-10 | 2024-01-26 | 华北理工大学 | Device for treating copper slag and method for treating copper slag |
| CN113249594B (en) * | 2020-12-24 | 2022-09-06 | 国家地质实验测试中心 | Method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore |
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|---|---|---|---|---|
| US3770414A (en) * | 1970-12-28 | 1973-11-06 | Continental Ore Corp | Recovery of rhenium and molybdenum values from molybdenite concentrates |
| CN102703715A (en) * | 2012-06-26 | 2012-10-03 | 西部鑫兴金属材料有限公司 | Method for recovering rhenium and molybdenum from rhenium and molybdenum-containing concentrate calcination flue dust |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770414A (en) * | 1970-12-28 | 1973-11-06 | Continental Ore Corp | Recovery of rhenium and molybdenum values from molybdenite concentrates |
| CN102703715A (en) * | 2012-06-26 | 2012-10-03 | 西部鑫兴金属材料有限公司 | Method for recovering rhenium and molybdenum from rhenium and molybdenum-containing concentrate calcination flue dust |
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