CN106834674A - Method for oxygen pressure leaching of uranium and molybdenum from uranium molybdenum ore - Google Patents
Method for oxygen pressure leaching of uranium and molybdenum from uranium molybdenum ore Download PDFInfo
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- CN106834674A CN106834674A CN201611246386.XA CN201611246386A CN106834674A CN 106834674 A CN106834674 A CN 106834674A CN 201611246386 A CN201611246386 A CN 201611246386A CN 106834674 A CN106834674 A CN 106834674A
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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
- 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
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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
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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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
- C22B60/0226—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors
- C22B60/0234—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors sulfurated ion as active agent
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Abstract
The invention discloses a method for leaching uranium and molybdenum from uranium molybdenum ore by oxygen pressure, and belongs to the technical field of comprehensive recycling of uranium and molybdenum. Aiming at uranium-molybdenum ores with variable properties, the invention effectively oxidizes the molybdenum-colloid ores in the uranium-molybdenum ores by using oxygen or oxygen in the air at a certain temperature, effectively realizes the enhanced leaching of uranium and molybdenum, greatly improves the recovery rate of Mo, and practically solves the problems of serious molybdenum resource waste and serious secondary pollution in the prior uranium-molybdenum industrial development. The method has wide adaptability to uranium molybdenum ores, can efficiently leach uranium and molybdenum from the uranium molybdenum ores, uranium molybdenum ore normal-pressure sulfuric acid leaching residues and single molybdenum ores, and realizes green and efficient recovery of uranium and molybdenum resources.
Description
Technical field
The invention belongs to uranium, molybdenum Comprehensive Recovery Technology field, it is related to a kind of uranium molybdenum ore oxygen leaching uranium, the method for molybdenum, has
Body is related to uranium, the method for molybdenum in oxygen leaching uranium molybdenum ore.
Background technology
Uranium molybdenum ore existence form is complicated, except molybdenum ore things such as molybdine molybdite, ferrimolybdite, molybdenum calcium ore deposit, wulfenites, in such ore also
The molybdenum ore thing of a kind of special shape of generally existing-jordisite, i.e. agglutination, the homogeneous amorphous matter of spherolite output, colloid
MoS2, caused by the order of interior generation ore deposit, in black fine powdered or noncrystalline, the colloid MoS of gluey output2, it is often table
Rawore is attached to molybdenum ore or the surface of other ores, and the sulfide parcel of densification is formed to accompanying ore, hinders leaching
Go out agent to the infiltration inside inclusion enclave and oxidant to uranium, the oxidation of molybdenum ore thing, increased the leaching difficulty of uranium and molybdenum.
The conventional processing method of existing uranium molybdenum ore has：Conventional acidleach, conventional alkali leaching, alkaline pressure of oxygen leaching, mix acid and the method such as cure.
, using sulfuric acid or alkali as leaching agent, hydrogen peroxide, pyrolusite or potassium permanganate etc. are used as oxidant, heating for conventional acidleach or alkali leaching
Leaching, is influenceed by ore properties, and molybdenum leaching rate is changed greatly, in 30%~70% fluctuation.Simultaneous oxidation agent consumption is occupied
It is high not under, domestic certain smelting enterprise, as oxidant, the 12% of ore amount is reached during dioxygen water consumption highest using hydrogen peroxide,
Nearly 40,000,000 yuan of dioxygen water consumption of year；In recent years, molybdenum valency is low, and enterprise is difficult to bear, can only be using reduction dioxygen water consumption
Leaching way, but the leaching rate of molybdenum is too low, less than 40%, problem core is to be difficult to the efficient oxidation in jordisite, causes molybdenum
Can not be leached and enter solution, in there is Tailings Dam into heap in uranium molybdenum ore leached mud in about 60% molybdenum and 15% uranium, one side uranium,
Mo resource serious waste, is rich in substantial amounts of uranium molybdenum in another aspect uranium molybdenum ore leached mud, environmental risk is severe.Using pressurization alkali
Leaching, molybdenum leaching rate can reach 80% or so, but the method has reagent consumption greatly, and the operation and maintenance cost of overhaul is higher, ore deposit
The problems such as slurry separation of solid and liquid is difficult, while NaOH can not be circulated, it is necessary to all with Na in systems2SO4Form open circuit, it is impossible to
The circulation of the solution of hydrometallurgical processes is realized, the technique only has the meaning of scientific research, the value without commercial Application；Using sulphur
Ore deposit curing is mixed in acid, and nitric acid or sodium chlorate assisted oxidation carry out the synthetical recovery of uranium molybdenum, and it is left that the method molybdenum leaching rate can reach 80%
The right side, but at present due to environmental requirement, process water needs Returning utilization, and nitrate anion and chlorine root are difficult to economic removal, so being difficult to
Implement again.
Additionally, association molybdenum ore of the output uranium-bearing grade less than 0.03% is referred to as single molybdenum ore, uranium-bearing in uranium molybdenum ore development process
The embedding cloth of molybdenum ore thing is extremely fine, has no that, in the mineral of crystalline form, floatability is very poor based on gluey mineral, under microscope.Main mine
Thing is limonite, pyrite, molybdenum calcium ore deposit, uranium molybdenum ore, and gangue mineral is mainly quartz, clay mineral and feldspar.Molybdenum is main with oxygen
The form preservation of compound accounts for the 80% of total molybdenum in limonite, partly with molybdenum calcium ore deposit, uranium molybdenum ore, ilsemannite and jordisite
Form exist.Corase grind is unable to monomer dissociation, fine grinding then easy argillization, it is difficult to the richness of uranium, molybdenum is effectively realized by way of ore dressing
Collection.Cost-effective synthetical recovery mode is industrially there is no at present, based on storing up, domestic certain enterprise is for the single molybdenum ore for producing
Accumulative to store up nearly 20,000,000 tons, environmental pollution is serious.
In sum, uranium molybdenum ore (containing single molybdenum ore) is used as a kind of important uranium of China, Mo resource, due to lack effective uranium,
Molybdenum leaches separation method, causes uranium, molybdenum leaching rate unstable, and molybdenum comprehensive recovery is low, the technology road that current enterprise uses
Line serious waste of resources, secondary environmental risk is severe, it would be highly desirable to which exploitation has the green, efficient of extensive adaptability for uranium molybdenum ore
Uranium molybdenum New Technology for Comprehensive Recovery, so as to realize the high efficient resourcing of uranium molybdenum ore, uranium molybdenum ore normal pressure sulfuric acid leaching slag and single molybdenum ore
Utilize.
The content of the invention
The present invention is for existing uranium molybdenum ore extract technology ore bad adaptability, uranium molybdenum leaching rate be low, uranium Mo resource wastes tight
The severe problem of weight, secondary environmental risk, through exploration discovery under sulfuric acid system uranium molybdenum ore oxygen leaching new technology, in a constant temperature
Degree is lower can to realize the deep oxidation of uranium in uranium molybdenum ore, molybdenum by the oxygen in oxygen or air, and then realizes the efficient leaching of uranium, molybdenum
Go out, Uranium extraction rate is promoted to 95% from the 85% of common process, and molybdenum leaching rate is promoted to 90% from the 40% of common process.Need not
The other oxidants of addition, significantly reduce uranium, the cost of molybdenum leaching process, effectively improve the competition of uranium molybdenum ore processing enterprise
Power.
The purpose of the present invention is achieved through the following technical solutions.
A kind of uranium molybdenum ore oxygen leaching uranium of the invention, the method for molybdenum, it is characterised in that comprise the following steps：
(1) uranium molybdenum ore is crushed be finely ground to granularity be -0.5mm~-0.037mm account for more than 90% (granularity represent in "-"
Represent below certain granularity)；
(2) after the uranium molybdenum ore after the fine grinding for obtaining step (1) mixes with leachate in a kettle. at a certain temperature
Oxygen leaching uranium, molybdenum are carried out, then separation of solid and liquid, Uranium extraction rate is carried out to leaching ore pulp>95%, molybdenum oxygenation efficiency>99%；
(3) to obtained by step (2) rich in uranium, molybdenum solution using existing conventional method carry out solvent extraction extract uranium,
Molybdenum.
Further, leachate is to contain H described in step (2)2SO4The aqueous solution, wherein H2SO4Concentration 2g/L~
300g/L, preferably H2SO4Concentration 15g/L~50g/L.
Further, it is 1~6 that liquid-solid ratio (volume mass ratio) is leached described in step (2):1L/kg.
Further, extraction temperature described in step (2) is 100 DEG C~200 DEG C, and preferable temperature is 140 DEG C~170 DEG C.
Far below 220 DEG C~250 DEG C of conventional molybdenum concntrate oxygen leaching temperature.
Further, oxidant is O in leaching process described in step (2)2Or the oxygen in air, partial pressure of oxygen be 0.02~
1.0MPa, preferably partial pressure of oxygen are 0.1~0.5MPa.Compared to conventional molybdenum concntrate oxygen leaching, without adding nitric acid or nitrate
Used as oxidant, subsequent treatment process need not consider the treatment of ammonia nitrogen waste water, be conducive to solution in whole uranium molybdenum recovery system
Circulation.
Further, extraction time described in step (2) is 0.5h~6h.
Further, uranium, the leaching of molybdenum in uranium molybdenum ore are applicable not only to, are also suitable in uranium molybdenum ore normal pressure sulfuric acid leaching slag
Uranium, the leaching of molybdenum in the leaching of uranium, molybdenum, and single molybdenum ore of uranium molybdenum ore association.
A kind of uranium molybdenum ore oxygen leaching uranium of the invention, the method for molybdenum, it is advantageous that：For the changeable uranium of Mo, S property
Molybdenum ore, in the case where not doing significantly change to existing industrial process stream, not increasing processing cost, the guarantee U rate of recovery, can be big
Width improves the rate of recovery of Mo, can effectively process uranium molybdenum ore, uranium molybdenum ore normal pressure sulfuric acid leaching slag and single molybdenum ore, solves conscientiously current
Mo resource present in uranium molybdenum ore commercial development wastes serious problem.
Brief description of the drawings
Fig. 1 is the principle process chart of the inventive method.
Specific embodiment
The present invention is made below in conjunction with accompanying drawing being further illustrated.
The method of the present invention is further described with nonlimiting examples below, to help to understand of the invention
Content and its advantage, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
Uranium molybdenum ore in embodiment is the uranium molybdenum ore employed in certain uranium smelting enterprise industrial production, its composition such as following table：
| Element | U | Mo | Fe | Al | S | |
| Uranium molybdenum ore/% | 0.105 | 0.85 | 3.62 | 6.25 | 60.09 | 6.7 |
| Uranium molybdenum ore leached mud % | 0.018 | 0.57 | 0.55 | 1.28 | 67.21 | 3.2 |
| Single molybdenum/% ore deposits/% | 0.028 | 0.26 | 3.22 | 5.22 | 77.83 | 0.16 |
Embodiment 1
Uranium molybdenum ore is crushed be finely ground to granularity -0.074mm account for more than 90%, leachate is 50g/L H2SO4Solution, leaching
Go out 160 DEG C of temperature, oxidant is O2, leaching process O2Partial pressure 0.3MPa, liquid-solid ratio is 3:1, extraction time 3h, molybdenum oxygenation efficiency
99%, Uranium extraction rate 98%.After leaching solid-liquid separation on ore pulp, leachate reclaims uranium molybdenum, leached mud using solvent-extracted method
Tailings reservoir for piling is sent after washing, leached mud wash water is incorporated to leachate and reclaims uranium molybdenum or return to configuration leachate.
Embodiment 2
Uranium molybdenum ore is crushed be finely ground to granularity -0.045mm account for more than 90%, leachate is 100g/L H2SO4Solution, leaching
Go out 180 DEG C of temperature, oxidant is O2, leaching process O2Partial pressure 0.3MPa, liquid-solid ratio is 5:1, extraction time 2h, molybdenum oxygenation efficiency
99%, Uranium extraction rate 96%.After leaching solid-liquid separation on ore pulp, leachate reclaims uranium molybdenum, leached mud using solvent-extracted method
Tailings reservoir for piling is sent after washing, leached mud wash water is incorporated to leachate and reclaims uranium molybdenum.
Embodiment 3
Uranium molybdenum ore is crushed be finely ground to granularity -0.037mm account for more than 90%, leachate is 150g/L H2SO4Solution, leaching
Go out 140 DEG C of temperature, oxidant is O2, leaching process O2Partial pressure 0.5MPa, liquid-solid ratio is 5:1, extraction time 6h, molybdenum oxygenation efficiency
99%, Uranium extraction rate 96%.After leaching solid-liquid separation on ore pulp, leachate reclaims uranium molybdenum, leached mud using solvent-extracted method
Tailings reservoir for piling is sent after washing, leached mud wash water is incorporated to leachate and reclaims uranium molybdenum.
Embodiment 4
Uranium molybdenum ore normal pressure sulfuric acid leaching slag is crushed be finely ground to granularity -0.037mm account for more than 90%, leachate is 50g/
L H2SO4Solution, 160 DEG C of extraction temperature, oxidant is O2, leaching process O2Partial pressure 0.1MPa, liquid-solid ratio is 2.5:1, during leaching
Between 3h, molybdenum oxygenation efficiency 99%,.After leaching solid-liquid separation on ore pulp, leachate reclaims uranium molybdenum, leached mud using solvent-extracted method
Tailings reservoir for piling is sent after washing, leached mud wash water is incorporated to leachate and reclaims uranium molybdenum.
Embodiment 5
Uranium molybdenum ore normal pressure sulfuric acid leaching slag is crushed be finely ground to granularity -0.074mm account for more than 90%, leachate is 20g/
L H2SO4Solution, 150 DEG C of extraction temperature, oxidant is O2, leaching process O2Partial pressure 0.2MPa, liquid-solid ratio is 2.5:1, during leaching
Between 3h, molybdenum oxygenation efficiency 99%.After leaching solid-liquid separation on ore pulp, leachate reclaims uranium molybdenum, leached mud using solvent-extracted method
Tailings reservoir for piling is sent after washing, leached mud wash water is incorporated to leachate and reclaims uranium molybdenum.
Embodiment 6
Single molybdenum ore is crushed be finely ground to granularity -0.074mm account for more than 90%, leachate is 50g/L H2SO4Solution, leaching
Go out 150 DEG C of temperature, oxidant is O2, leaching process O2Partial pressure 0.2MPa, liquid-solid ratio is 2.5:1, extraction time 3h, molybdenum oxygenation efficiency
99%.After leaching solid-liquid separation on ore pulp, leachate reclaims uranium molybdenum using solvent-extracted method, and Tailings Dam is sent after leached mud washing
Store up, leached mud wash water is incorporated to leachate and reclaims uranium molybdenum.
Embodiment 7
Single molybdenum ore is crushed be finely ground to granularity -0.045mm account for more than 90%, leachate is 100g/L H2SO4Solution, leaching
Go out 170 DEG C of temperature, oxidant is O2, leaching process O2Partial pressure 0.2MPa, liquid-solid ratio is 3.5:1, extraction time 3h, molybdenum oxygenation efficiency
99%.After leaching solid-liquid separation on ore pulp, leachate reclaims uranium molybdenum using solvent-extracted method, and Tailings Dam is sent after leached mud washing
Store up, leached mud wash water is incorporated to leachate and reclaims uranium molybdenum.
Claims (7)
1. a kind of uranium molybdenum ore oxygen leaching uranium, the method for molybdenum, it is characterised in that comprise the following steps：
(1) it is that -0.5mm~-0.037mm accounts for more than 90% to crush uranium molybdenum ore and to be finely ground to granularity；
(2) the uranium molybdenum ore after the fine grinding for obtaining step (1) is carried out at a certain temperature in a kettle. after mixing with leachate
Oxygen leaching uranium, molybdenum, then carry out separation of solid and liquid to leaching ore pulp；
(3) solvent extraction is carried out using existing conventional method to the solution rich in uranium, molybdenum obtained by step (2) and extracts uranium, molybdenum.
2. method according to claim 1, it is characterised in that leachate is to contain H described in step (2)2SO4It is water-soluble
Liquid；Wherein H2SO4Concentration 2g/L~300g/L, preferably H2SO4Concentration 15g/L~50g/L.
3. method according to claim 1, it is characterised in that it is 1~6 that liquid-solid ratio is leached described in step (2):1L/kg.
4. method according to claim 1, it is characterised in that extraction temperature described in step (2) is 100 DEG C~200 DEG C,
Preferable temperature is 140 DEG C~170 DEG C.
5. method according to claim 1, it is characterised in that oxidant is O in leaching process described in step (2)2Or it is empty
Oxygen in gas, partial pressure of oxygen is 0.02~1.0MPa, and preferably partial pressure of oxygen is 0.1~0.5MPa.
6. method according to claim 1, it is characterised in that extraction time described in step (2) is 0.5h~6h.
7. method according to claim 1, it is characterised in that be applicable not only to uranium, the leaching of molybdenum in uranium molybdenum ore, be also suitable for
Uranium, the leaching of molybdenum in uranium, the leaching of molybdenum, and single molybdenum ore of uranium molybdenum ore association in uranium molybdenum ore normal pressure sulfuric acid leaching slag.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110714119A (en) * | 2018-12-19 | 2020-01-21 | 中核沽源铀业有限责任公司 | Oxygen pressure acid leaching industrialization method for primary uranium molybdenum ore |
| CN111349782A (en) * | 2020-04-15 | 2020-06-30 | 中核沽源铀业有限责任公司 | Method for improving filtering efficiency of complex molybdenum ore direct leaching ore pulp |
| CN111455172A (en) * | 2020-04-15 | 2020-07-28 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
| CN114058860A (en) * | 2021-11-26 | 2022-02-18 | 中国地质科学院郑州矿产综合利用研究所 | Method for comprehensively recycling uranium and molybdenum from uranium and molybdenum extraction third-phase filter residue |
| CN115852140A (en) * | 2022-12-26 | 2023-03-28 | 核工业北京化工冶金研究院 | Comprehensive extraction method of complex uranium molybdenum ore |
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| CN105420488A (en) * | 2015-12-30 | 2016-03-23 | 核工业北京化工冶金研究院 | Method for preprocessing wrapped uranium-molybdenum ores through oxidizing roasting |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110714119A (en) * | 2018-12-19 | 2020-01-21 | 中核沽源铀业有限责任公司 | Oxygen pressure acid leaching industrialization method for primary uranium molybdenum ore |
| CN110714119B (en) * | 2018-12-19 | 2021-09-17 | 中核沽源铀业有限责任公司 | Oxygen pressure acid leaching industrialization method for primary uranium molybdenum ore |
| CN111349782A (en) * | 2020-04-15 | 2020-06-30 | 中核沽源铀业有限责任公司 | Method for improving filtering efficiency of complex molybdenum ore direct leaching ore pulp |
| CN111455172A (en) * | 2020-04-15 | 2020-07-28 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
| CN111349782B (en) * | 2020-04-15 | 2022-04-22 | 中核沽源铀业有限责任公司 | Method for improving filtering efficiency of complex molybdenum ore direct leaching ore pulp |
| CN111455172B (en) * | 2020-04-15 | 2022-05-06 | 中核沽源铀业有限责任公司 | Method for efficiently utilizing complex molybdenum ore by self-circulation of wastewater |
| CN114058860A (en) * | 2021-11-26 | 2022-02-18 | 中国地质科学院郑州矿产综合利用研究所 | Method for comprehensively recycling uranium and molybdenum from uranium and molybdenum extraction third-phase filter residue |
| CN115852140A (en) * | 2022-12-26 | 2023-03-28 | 核工业北京化工冶金研究院 | Comprehensive extraction method of complex uranium molybdenum ore |
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