CN106477630A - A kind of oxygen presses the method that water seaoning processes molybdenite coproduction ammonium molybdate and sulphuric acid - Google Patents

A kind of oxygen presses the method that water seaoning processes molybdenite coproduction ammonium molybdate and sulphuric acid Download PDF

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CN106477630A
CN106477630A CN201610906901.6A CN201610906901A CN106477630A CN 106477630 A CN106477630 A CN 106477630A CN 201610906901 A CN201610906901 A CN 201610906901A CN 106477630 A CN106477630 A CN 106477630A
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filtrate
molybdenite
molybdenum
ammonium molybdate
oxygen
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CN106477630B (en
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徐红彬
付云枫
李晓艳
肖清贵
张懿
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Institute of Process Engineering of CAS
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00Compounds of molybdenum
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/69Sulfur trioxide; Sulfuric acid
    • C01B17/74Preparation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Abstract

The present invention provides a kind of oxygen to press the method that water seaoning processes molybdenite coproduction ammonium molybdate and sulphuric acid, the method comprising the steps of:Molybdenite powder is pressed 1 with water:2~1:7 solid-to-liquid ratio mix homogeneously, makes molybdenite ore pulp;Molybdenite ore pulp is injected pressure reaction still and reacts so as to carry out oxygen pressure water logging with oxidizing gas;The slurry obtaining is filtered, is obtained filter cake and filtrate;By filter cake through ammonia leaching, filter, crystallize prepared ammonium molybdate product;After filtrate is processed through de- molybdenum, obtain sulfuric acid product.The method of the invention reaches more than 95% for the overall recovery of molybdenum, even as high as more than 98%, the sulphuric acid of higher concentration can be obtained simultaneously, and not generation environment pollution, simply, efficiently, energy-conservation, it is the hydrometallurgy process for cleanly preparing that a kind of eco-friendly efficient utilization molybdenite comes coproduction ammonium molybdate and sulphuric acid, there is good industrial applications prospect.

Description

A kind of oxygen presses the method that water seaoning processes molybdenite coproduction ammonium molybdate and sulphuric acid
Technical field
The invention belongs to molybdenum chemical industry and field of hydrometallurgy, process molybdenite coproduction molybdenum particularly to a kind of oxygen pressure water seaoning Sour ammonium and the method for sulphuric acid.
Background technology
Molybdenite is the widest molybdenum ore of molybdenum industrial application, is the primary raw material producing ammonium molybdate and molybdenum oxide.At present should Produce, with molybdenite oxidizing roasting-ammonia soaking technology, the technique for applying that ammonium molybdate is ripe main flow, but this technique can produce greatly The SO of amount2Flue gas, the SO being produced due to the feature of equipment and technique itself2The most concentration of flue gas relatively low prepare sulfur it is impossible to reach The requirement of acid, SO2Flue gas is polluted environment by outer row.
Wet treatment molybdenite technique can preferably solve SO2Fume emission problem, a lot of scholars and enterprise have done greatly Quantifier elimination, the main method of current wet treatment molybdenite can be divided into electrochemical leaching method, acid oxidation to leach and alkaline process oxygen Change and leach.
CN101775491A disclose a kind of NaCl is used as the electrolytic method of medium, this electrochemical leaching method anti- Although answering temperature to be room temperature, and reaction medium being cheap and easy to get, current efficiency is only capable of 60% about.
The oxidant that acid oxidation leaches can be oxidizing gas or liquid oxidizer, this kind of process brightness molybdenum The method of ore deposit, such as the method disclosed in CN104745812A, using sulphuric acid as medium, nitric acid or oxygen as oxidant, instead Answer the acidity of system very big, the material requirement to consersion unit is more strict.
Sodium hydroxide being used as reaction medium the method for alkaline process oxidation processes molybdenite more, such as CN102534207A and The method of the alkaline process oxidation processes molybdenite disclosed in CN101956070A is although avoid lacking of concentrated acid severe corrosion equipment Point, does not have SO yet2Smoke pollution environment, but during the course of the reaction alkali except with molybdenum in molybdenite react also will with molybdenite in Reaction of Salmon-Saxl, and with the alkali consumption of reaction of Salmon-Saxl be the alkali consumption reacting with molybdenum twice, produce by-product cheap in a large number, Consumption alkali, seriously so that the economy of the method substantially reduces, constrains the commercial applications that oxygen presses alkaline leaching.
Additionally, somebody proposes to use water as the medium of oxygen leaching, such as CN103866142A discloses oxygen pressure water logging The method that molybdenite reclaims molybdenum and rhenium, using high liquid-solid ratio water logging molybdenite, the solid phase obtaining after leaching produces work after treatment Industry molybdenum trioxide, the liquid phase obtaining is used NaHS as impurity removal reagents, after the pH of regulation leachate is 7~8, removes precipitation Impurity out.Because acidity is stronger in the liquid phase after water logging, adjust pH using NaHS, the method for remove impurity can consume in a large number NaHS, also result in water logging generation sulphuric acid be neutralized into sodium sulfate byproduct, cause in reclaim liquid phase have valency become The high cost dividing.
Therefore, in the coproduction ammonium molybdate that a kind of environmental friendliness of exploitation is expected in this area, resource utilization is high, flow process is short and sulfur The method of acid.
Content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of oxygen pressure water seaoning processes molybdenite coproduction molybdenum Sour ammonium and the method for sulphuric acid.
For reaching this goal of the invention, the present invention employs the following technical solutions:
On the one hand, the present invention provides a kind of oxygen to press the method that water seaoning processes molybdenite coproduction ammonium molybdate and sulphuric acid, described Method comprises the following steps:
(1) molybdenite powder is pressed 1 with water:2~1:8 solid-to-liquid ratio mix homogeneously, makes molybdenite ore pulp;
(2) the molybdenite ore pulp that step (1) obtains is injected pressure reaction still so as to carry out oxygen pressure water with oxidizing gas Leaching reaction;
(3) slurry obtaining step (2) is filtered, and obtains filter cake and filtrate;
(4) filter cake that step (3) obtains is obtained ammonium molybdate product through ammonia leaching, filtration, crystallization;
(5), after step (3) gained filtrate being processed through de- molybdenum, obtain sulfuric acid product.
The present invention passes through to control in the larger context by the solid-to-liquid ratio of molybdenite powder and water, and that is, 1:2~1:7, thus reaching To the oxygenation efficiency of response speed and higher molybdenum faster, this and conventional wet-leaching molybdenite (acid system or alkaline process) method In low solid-to-liquid ratio be favorably improved the cognition of speed and have difference substantially, because water logging process is the process producing acid, necessarily The acid of concentration is favorably improved dissolubility in leachate for the oxygen, thus reaching the effect improving reaction rate, but in the past Water seaoning molybdenum when extracting, not this point consciously, the solid-to-liquid ratio of use is similar with common acid system and alkaline process low solid Liquor ratio, this not only reduces reaction rate, also can increase the molybdenum content in liquid phase, reduce the yield of reaction, also add reaction Inventory and increased energy consumption, improve production cost.Present invention contemplates that obtaining response speed faster, the higher sulfur of concentration Acid, thus add too many water can reduce the concentration of sulphuric acid, and the market price of dilute sulfuric acid is relatively low, higher in order to generate concentration It is desirable to oxygen is pressed using less water volume during water logging, the present invention passes through to the molybdenite being applied to preparation method of the present invention sulphuric acid The solid-to-liquid ratio of powder and water carries out screening and obtains in solid-to-liquid ratio being 1:2~1:7 (such as 1:2、1:2.5、1:2.8、1:3、1:3.5、1: 3.8、1:4、1:4.5、1:4.8、1:5、1:5.5、1:5.8、1:6、1:6.5、1:6.8 or 1:7), when, both can widen and use brightness The grade scope of molybdenum ore, the extraction ratio of guarantee molybdenum, can obtain the sulphuric acid of higher concentration again.
Preferably, in the described molybdenite powder of step (1), the weight/mass percentage composition of molybdenum is 25%~58%, such as 25%, 27%th, 29%, 31%, 33%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 54%, 56% or 58%, It is preferably 45%~58%, the present invention has widened the grade scope using molybdenite.
Preferably, granularity < 100 mesh of the described molybdenite powder of step (1), the such as granularity of molybdenite powder can be 120 Mesh, 140 mesh, 160 mesh, 180 mesh, 200 mesh, 210 mesh, 220 mesh, 230 mesh, 240 mesh, 260 mesh, 280 mesh, 300 mesh, 320 mesh, 400 mesh, 450 mesh, 500 mesh etc., preferably < 250 mesh.
Preferably, the described solid-to-liquid ratio of step (1) is 1:2~1:6, in the present invention solid-to-liquid ratio is controlled 1:2~1:6 When, so that the organic efficiency of molybdenum is higher, the concentration of the sulphuric acid in addition obtaining under this solid-to-liquid ratio is also higher.In the present invention Described solid-to-liquid ratio refers to the ratio of the quality (g) of solid and the volume (mL) of liquid.
Preferably, the described oxidizing gas of step (2) are any one in oxygen, air or ozone or at least two Mixture, preferably oxygen.
Preferably, the described oxygen of step (2) press water logging reaction temperature be 180 DEG C~220 DEG C, such as 180 DEG C, 185 DEG C, 187 DEG C, 190 DEG C, 195 DEG C, 198 DEG C, 200 DEG C, 205 DEG C, 208 DEG C, 210 DEG C, 215 DEG C or 220 DEG C, preferably 200 DEG C~220 ℃.
Preferably, the described oxygen of step (2) presses the oxygen partial pressure of water logging reaction is 0.5~2MPa, such as 0.5MPa, 0.8MPa, 1MPa, 1.2MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa or 2MPa, preferably 1~ 2MPa.If oxygen partial pressure is relatively low in the present invention, the speed of reaction can be made slower, be unfavorable for producing;If oxygen divides Pressure is higher but to increased the cost of high withstand voltage equipment although response speed can be improved, and therefore can control oxygen partial pressure In the scope of the present invention, and response speed and Cost Problems during preferably 1~2MPa, can be equalized, obtain preferable effect.
The oxygen partial pressure that the present invention uses can ensure that oxygen pressure water logging reaction obtains higher leaching in the short period of time Rate, thus improve production efficiency.
Preferably, the described oxygen of step (2) press water logging reaction time be 20min~4h, such as 20min, 25min, 30min, 40min, 50min, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.3h, 2.5h, 2.8h, 3h, 3.3h, 3.5h, 3.8h or 4h, It is preferably 1~4h, further preferred 1~2h.The present invention will control within the above range it is ensured that oxygen presses water logging in the response time The leaching rate of reaction is more than 95%.
In the present invention through the described oxygen of step (2) press water logging reaction so that molybdenite oxygenation efficiency 95% with On, such as 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98% or 99%.
Preferably, the Mo ion concentration in the described filtrate of step (3) be 0.1~80g/L, such as 0.1g/L, 0.5g/L, 1g/L, 2g/L, 5g/L, 8g/L, 10g/L, 15g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L or 80g/L.
Preferably, the H in the described filtrate of step (3)+Content be 0.1~10mol/L, such as 0.1mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L.
Preferably, the filter cake before the leaching of step (4) described ammonia, step (3) being obtained washs, and removes filter cake surface Attachment, obtain washing liquid.Preferably, described washing uses water as detergent.
Preferably, described washing liquid can return to molybdenite ore pulp preparation process as needed and recycle.
Preferably, in described washing liquid Mo ion concentration be 0.01~20g/L, such as 0.01g/L, 0.05g/L, 0.1g/L, 0.5g/L, 0.8g/L, 1g/L, 3g/L, 5g/L, 8g/L, 10g/L, 12g/L, 15g/L, 18g/L or 20g/L.
Preferably, H in described washing liquid+Content be 0.01~4mol/L, such as 0.01mol/L, 0.05mol/L, 0.08mol/L、0.1mol/L、0.5mol/L、0.8mol/L、1mol/L、1.5mol/L、2mol/L、2.5mol/L、3mol/L、 3.5mol/L or 4mol/L.
In the preparation process in accordance with the present invention, the molybdenum in described filtrate and washing liquid is deposited with complicated molybdate anion form Subsequent technique is being conducive to extract molybdenum ion from liquid phase.
Preferably, the leaching agent that the leaching of step (4) described ammonia uses is with NH3Count the ammonia that mass fraction is 20%~28% The mass fraction of water, such as ammonia is 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27% or 28%.
Preferably, the method that the described de- molybdenum of step (5) is processed is ion exchange or extraction.Described in the present invention de- Molybdenum refers to the process of get rid of the molybdate anion containing in filtrate.
Preferably, described ion exchange is to carry out ion exchange using anion exchange resin it is therefore an objective to by filtrate Molybdate anion separate from filtrate.
Preferably, described anion exchange resin be amido class macroporous weakly basic anion exchange resin, such as D314 or D301 etc..
Preferably, during described ion exchange, anion exchange resin and the mass volume ratio of filtrate are 1:6~1:60, for example 1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13、1:14、1:15、1:20、1:23、1:25、1:30、1:32、1:35、 1:38、1:40、1:45、1:50、1:55、1:58 or 1:60, preferably 1:6~1:25.
Preferably, temperature during described ion exchange be 0~80 DEG C, such as 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C, preferably 20~60 DEG C.
Preferably, the time of described ion exchange be 10min~5h, such as 10min, 20min, 30min, 40min, 50min, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, preferably 30min~3h.
Preferably, described extraction is using amine extractant, filtrate to be extracted, by cloudy for the molybdate in filtrate from Son extracts from filtrate.
Preferably, described amine extractant is three (the octyl- last of the ten Heavenly stems) alkyl tertiary amine.
Regulator can be added as needed in extraction process, for example, add sec-octyl alcohol and kerosene as regulator, right Molybdenum acid ion in filtrate is extracted.
Preferably, the temperature of described extraction be 0 DEG C~80 DEG C, such as 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C, preferably 20 DEG C~50 DEG C.
The present invention uses ion exchange or extraction to extract the molybdenum in solution from filtrate, has good excellent of selectivity The molybdenum extracting, while removing molybdenum in liquid phase, can be produced into high purity product ammonium molybdate by gesture.In addition this process simple, Efficiently, energy-conservation, is overcome the molybdenum necessary elder generation remove impurity being reclaimed using Traditional Method in leachate, reuses evaporative crystallization method and reclaim molybdenum, The shortcoming that high energy consumption, efficiency are low and operation is numerous and diverse.
As the preferred technical solution of the present invention, oxygen pressure water seaoning of the present invention processes molybdenite coproduction ammonium molybdate and sulfur The method of acid specifically includes following steps:
(1) molybdenite powder is pressed 1 with water:2~1:7 solid-to-liquid ratio mix homogeneously, makes molybdenite ore pulp;
(2) the molybdenite ore pulp that step (1) is obtained inject pressure reaction still so as to oxidizing gas 180 DEG C~ 220 DEG C, carry out oxygen pressure water logging reaction 20min~4h under 0.5~2MPa;
(3) slurry obtaining step (2) is filtered, and obtains filter cake and filtrate;
(4) filter cake obtaining step (3) is washed, remove filter cake surface attachment, and after through ammonia leaching, filter, Crystallization is obtained ammonium molybdate product;
(5) step (3) gained filtrate is carried out through ion exchange or extraction, after de- molybdenum process, obtain sulfuric acid product;
Described ion exchange is to utilize the mass volume ratio with filtrate to be 1:6~1:60 anion exchange resin is 0 Carry out ion exchange 10min~5h at~80 DEG C, the molybdate anion in filtrate is separated from filtrate;Described extraction Method is filtrate to be extracted at 0 DEG C~80 DEG C using amine extractant, and the molybdate anion in filtrate is extracted from filtrate Take out.
The present invention is the hydrometallurgy cleaning that a kind of eco-friendly efficient utilization molybdenite comes coproduction ammonium molybdate and sulphuric acid Production technology, has good industrial applications prospect.
Compared with prior art, the invention has the advantages that:
(1) present invention adopts and uses water as medium, reduces the extent of corrosion to equipment for the concentrated acid medium, also makes operating environment Well.
(2) present invention processes molybdenite by the way of pressure oxidation water logging, presses water logging, more than 90% brightness molybdenum through peroxide Ore deposit is changed into molybdic acid hydrate and proceeds to solid phase, comprises only the hydrate of molybdic acid in solid phase in addition to containing a small amount of silicon dioxide, Ammonia soaking technology can directly be continued to use and prepare ammonium molybdate product.Copper in molybdenite, ferrum, lead and other elements proceed to liquid with cationic form Phase, without being mixed into solid phase with molybdic acid hydrate in the form of molybdate, the method for the present invention can obtain highly purified molybdic acid Ammonium product so that in molybdenite the overall recovery of molybdenum reach more than 95%, even as high as more than 98%.
(3) present invention adopts hydrometallurgy cleaning procedure to process molybdenite, it is to avoid SO2The discharge of flue gas, eliminates cigarette The pollution to environment for the gas.
(4) present invention uses ion exchange or extraction to reclaim the molybdenum ion in water-leach liquor, and flow process is short, efficiency Height, and the pH value of filtrate need not be adjusted during ion exchange or extraction.
(5) Mo resource in molybdenite is not only made full use of by the present invention, also the Sulphur ressource in molybdenite is changed into sulfur Acid is it is achieved that the high-efficiency cleaning of molybdenite resource utilizes.
Brief description
Fig. 1 utilizes oxygen to press water seaoning to process the process flow diagram of molybdenite coproduction ammonium molybdate and sulphuric acid for the present invention.
Fig. 2 is scanning electron microscope (SEM) figure of ammonium molybdate product of the present invention, and scale is 10 μm.
Fig. 3 is X-ray diffraction (XRD) figure of ammonium molybdate product of the present invention.
Specific embodiment
To further illustrate technical scheme below by specific embodiment.Those skilled in the art should be bright , described embodiment is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
In the present embodiment, it is prepared by the following method process molybdenite coproduction ammonium molybdate and sulphuric acid, specifically include following Step (its schematic flow sheet is as shown in Figure 1):
(1) the molybdenite powder containing molybdenum 45% less than 250 purposes is pressed solid-to-liquid ratio 1 with water:2(g:ML) mix homogeneously, makes Molybdenite ore pulp;
(2) molybdenite is starched injection pressure reaction still, at a temperature of 200 DEG C, enter with the oxidizing gas for 1MPa for the partial pressure Row oxygen pressure water logging reaction 1.5h;
(3) slurry obtaining step (2) is filtered, and obtains filter cake and filtrate;
(4) filter cake that step (3) obtains is obtained ammonium molybdate product through ammonia leaching, filtration, crystallization;
(5) step (3) gained filtrate is carried out de- molybdenum to process, filtrate need not adjust pH value, hand over using weakly-basic anion Change resin D301 and carry out anion exchange reaction, D301 is 1 with the solid-to-liquid ratio of filtrate:15(g:ML), 40 DEG C of temperature, the time is 120min, using 25%~28% ammonia (with NH3Count) resin is carried out with desorbing (regeneration), temperature is 40 DEG C, and desorption time is 1h, desorbing obtains pure ammonium molybdate solution, and the resin after desorbing, can be obtained after filtrate is taken off with molybdenum process with recycling Sulphuric acid, the concentration of gained sulphuric acid is 23.88%.
Water logging in the present embodiment goes out molybdenum in product to be existed with molybdic acid hydrate form, is computed understanding, the oxygenation efficiency of molybdenum is 98.86%;In the present embodiment, by filter cake, the quality purity through ammonia leaching, filtration, the prepared ammonium molybdate product of crystallization processes is 99.13%;In the present embodiment, by filtrate, the quality purity through the prepared ammonium molybdate product of ion-exchange process is 99.30%.This reality The overall recovery applying molybdenum in example is 98.24%.
Characterized using the ammonium molybdate product that scanning electron microscope (JSM-7610F, JEOL) prepares to the present embodiment, Result is as shown in Fig. 2 the ammonium molybdate as can be seen from the figure prepared is in bar-shaped and favorable dispersibility.
Carried out using the ammonium molybdate product that X-ray diffractometer (Phillips PW 223/30) prepares to embodiment Characterize, result as shown in figure 3, as can be seen from the figure the structure of ammonium molybdate more complete.
Embodiment 2
In the present embodiment, it is prepared by the following method process molybdenite coproduction ammonium molybdate and sulphuric acid, specifically include following Step (its schematic flow sheet is as shown in Figure 1):
(1) the molybdenite powder containing molybdenum 58% less than 250 mesh is pressed solid-to-liquid ratio 1 with water:7(g:ML) mix homogeneously, makes brightness Molybdenum ore ore pulp;
(2) molybdenite is starched injection pressure reaction still, at a temperature of 180 DEG C, with the oxidizing gas for 1.5MPa for the partial pressure Carry out oxygen pressure water logging reaction 4h;
(3) slurry obtaining step (2) is filtered, and obtains filter cake and filtrate;
(4) filter cake that step (3) obtains is obtained ammonium molybdate product through ammonia leaching, filtration, crystallization;
(5) step (3) gained filtrate is carried out de- molybdenum to process, filtrate need not adjust pH value, hand over using weakly-basic anion Change resin D301 and carry out anion exchange reaction, D301 is 1 with the solid-to-liquid ratio of filtrate:6(g:ML), 40 DEG C of temperature, the time is 50min, using 25%~28% ammonia (with NH3Count) resin is carried out with desorbing (regeneration), temperature is 40 DEG C, and desorption time is 1h, the resin after desorbing can obtain sulphuric acid, the concentration of gained sulphuric acid is with recycling after filtrate is taken off with molybdenum process 10.32%.
Water logging in the present embodiment goes out molybdenum in product to be existed with molybdic acid hydrate form, is computed understanding, the oxygenation efficiency of molybdenum is 97.91%;It is 99.42% by the quality purity through ammonia leaching, filtration, the prepared ammonium molybdate product of crystallization processes for the filter cake;The present embodiment In by filtrate through ion-exchange process be obtained ammonium molybdate product quality purity be 99.80%.Total recovery of molybdenum in the present embodiment Rate is 95.11%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to the ammonium molybdate product obtaining, and again show that The ammonium molybdate arriving is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 3
In the present embodiment, it is prepared by the following method process molybdenite coproduction ammonium molybdate and sulphuric acid, specifically include following Step (its schematic flow sheet is as shown in Figure 1):
(1) the molybdenite powder containing molybdenum 47% less than 100 mesh is pressed solid-to-liquid ratio 1 with water:6(g:ML) mix homogeneously, makes brightness Molybdenum ore ore pulp;
(2) molybdenite slurry liquid is injected pressure reaction still, at a temperature of 220 DEG C, with the oxidisability for 0.5MPa for the partial pressure Gas carries out oxygen pressure water logging reaction 2h;
(3) above-mentioned second step gained slurry is filtered, obtained filter cake and filtrate;
(4) filter cake after washing is through prepared ammonium molybdate products such as ammonia leaching, filtration, crystallizations;
(5) filtrate obtained by above-mentioned 3rd step is carried out de- molybdenum to process, filtrate need not adjust filtrate pH value, using weak base Property anion exchange resin D301 carry out anion exchange reaction, solid-to-liquid ratio be 1:6(g:ML), 30 DEG C of temperature, the time is 2h, makes With 25%~28% ammonia (with NH3Count) resin is carried out with desorbing (regeneration), temperature is 40 DEG C, and desorption time is 1h, after desorbing Resin filtrate can be taken off after molybdenum processes, obtain sulphuric acid, the concentration of gained sulphuric acid is 9.75% with recycling.
Water logging in the present embodiment goes out molybdenum in product to be existed with molybdic acid hydrate form, is computed understanding, the oxygenation efficiency of molybdenum is 95.79%;It is 99.52% by the quality purity through the prepared ammonium molybdate product of the techniques such as ammonia leaching, filtration, crystallization for the filter cake;By filtrate The quality purity that ammonium molybdate product is obtained through techniques such as ion exchanges is 99.79%, and in the present embodiment, the overall recovery of molybdenum is 96.01%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to the ammonium molybdate product obtaining, and again show that The ammonium molybdate arriving is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 4
In the present embodiment, it is prepared by the following method process molybdenite coproduction ammonium molybdate and sulphuric acid, specifically include following Step (its schematic flow sheet is as shown in Figure 1):
(1) the 54% molybdenite powder less than 250 mesh is pressed solid-to-liquid ratio 1 with water:2(g:ML) mix homogeneously, makes molybdenite Ore pulp;
(2) molybdenum concntrate ore pulp feed liquid is injected pressure reaction still, at a temperature of 180 DEG C, with the oxidisability for 2MPa for the partial pressure Gas carries out oxygen pressure water logging reaction 180min;
(3) above-mentioned second step gained slurry is filtered, obtained filter cake and filtrate;
(4) filter cake after washing is through prepared ammonium molybdate products such as ammonia leaching, filtration, crystallizations;
(5) filtrate obtained by above-mentioned 3rd step is carried out de- molybdenum to process, filtrate need not adjust filtrate pH value, using weak base Property anion exchange resin D301 carry out anion exchange reaction, solid-to-liquid ratio be 1:6(g:ML), 40 DEG C of temperature, the time is 50min, using 25%~28% ammonia (with NH3Count) resin is carried out with desorbing (regeneration), temperature is 40 DEG C, and desorption time is 1h, the resin after desorbing can obtain sulphuric acid, the concentration of gained sulphuric acid is with recycling after filtrate is taken off with molybdenum process 25.12%.
Water logging in the present embodiment goes out molybdenum in product to be existed with molybdic acid hydrate form, is computed understanding, the oxygenation efficiency of molybdenum is 96.17%;In the present embodiment, by filter cake, the quality purity through ammonia leaching, filtration, the prepared ammonium molybdate product of crystallization processes is 99.48%;In the present embodiment, by filtrate, the quality purity through the prepared ammonium molybdate product of ion-exchange process is 99.88%.This reality The overall recovery applying molybdenum in example is 97.59%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to the ammonium molybdate product obtaining, and again show that The ammonium molybdate arriving is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 5
In the present embodiment, it is prepared by the following method process molybdenite coproduction ammonium molybdate and sulphuric acid, specifically include following Step (its schematic flow sheet is as shown in Figure 1):
(1) the 56% molybdenite powder less than 250 mesh is pressed solid-to-liquid ratio 1 with water:5(g:ML) mix homogeneously, makes molybdenite Ore pulp;
(2) molybdenum concntrate ore pulp feed liquid is injected pressure reaction still, at a temperature of 220 DEG C, with the oxidisability for 2MPa for the partial pressure Gas carries out oxygen pressure water logging reaction 60min;
(3) above-mentioned second step gained slurry is filtered, obtained filter cake and filtrate;
(4) filter cake after washing is through prepared ammonium molybdate products such as ammonia leaching, filtration, crystallizations;
(5) filtrate obtained by above-mentioned 3rd step is carried out de- molybdenum to process, filtrate need not adjust filtrate pH value, using weak base Property anion exchange resin D301 carry out anion exchange reaction, solid-to-liquid ratio be 1:6(g:ML), 40 DEG C of temperature, the time is 50min, using 25%~28% ammonia (with NH3Count) resin is carried out with desorbing (regeneration), temperature is 40 DEG C, and desorption time is 1h, the resin after desorbing can obtain sulphuric acid, the concentration of gained sulphuric acid is with recycling after filtrate is taken off with molybdenum process 11.67%.
Water logging in the present embodiment goes out molybdenum in product to be existed with molybdic acid hydrate form, is computed understanding, the oxygenation efficiency of molybdenum is 99.91%;In the present embodiment, by filter cake, the quality purity through ammonia leaching, filtration, the prepared ammonium molybdate product of crystallization processes is 99.15%;In the present embodiment, by filtrate, the quality purity through the prepared ammonium molybdate product of ion-exchange process is 99.87%.This reality The overall recovery applying molybdenum in example is 99.47%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to the ammonium molybdate product obtaining, and again show that The ammonium molybdate arriving is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 6
The present embodiment and embodiment 2 differ only in step (1) molybdenite powder and water by solid-to-liquid ratio 1:4 mixing, remove Outside this, remaining preparation process and condition select all same as Example 2.Water logging in the present embodiment goes out in product molybdenum to be hydrated Molybdic acid exists, and is computed understanding, the oxygenation efficiency of molybdenum is 99.64%;Molybdenum is obtained through ammonia leaching, filtration, crystallization processes by filter cake The quality purity of sour ammonium product is 99.59%;The matter of ammonium molybdate product is obtained through ion-exchange process by filtrate in the present embodiment Amount purity is 99.81%.In the present embodiment, the overall recovery of molybdenum is 98.43%, and the concentration of gained sulphuric acid is 18.28%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to the ammonium molybdate product obtaining, and again show that The ammonium molybdate arriving is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 7
The present embodiment is 25% with the grade (i.e. molybdenum content) differing only in molybdenite powder in step (1) of embodiment 2, In addition, remaining preparation process and condition selection are all same as Example 2.Water logging in the present embodiment goes out in product molybdenum with water Close molybdic acid to exist, be computed understanding, the oxygenation efficiency of molybdenum is 99.32%;It is obtained through ammonia leaching, filtration, crystallization processes by filter cake The quality purity of ammonium molybdate product is 99.10%;In the present embodiment, ammonium molybdate product is obtained through ion-exchange process by filtrate Quality purity is 99.72%.In the present embodiment, the overall recovery of molybdenum is 97.93%, and the concentration of gained sulphuric acid is 14.23%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to the ammonium molybdate product obtaining, and again show that The ammonium molybdate arriving is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 8
The present embodiment is 30% with the grade (i.e. molybdenum content) differing only in molybdenite powder in step (1) of embodiment 2, In addition, remaining preparation process and condition selection are all same as Example 2.Water logging in the present embodiment goes out in product molybdenum with water Close molybdic acid to exist, be computed understanding, the oxygenation efficiency of molybdenum is 98.96%;It is obtained through ammonia leaching, filtration, crystallization processes by filter cake The quality purity of ammonium molybdate product is 99.15%;In the present embodiment, ammonium molybdate product is obtained through ion-exchange process by filtrate Quality purity is 99.37%.In the present embodiment, the overall recovery of molybdenum is 97.55%, and the concentration of gained sulphuric acid is 17.48%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to the ammonium molybdate product obtaining, and again show that The ammonium molybdate arriving is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 9
The present embodiment uses 20% 3 (the octyl- last of the ten Heavenly stems) alkyl tertiary amine (N235) to make with the step (5) that differs only in of embodiment 2 For extractant, de- molybdenum process, extractant and leaching filtrate body are carried out as regulator using 10% sec-octyl alcohol+70% kerosene to filtrate Long-pending ratio is 1:5,40 DEG C of temperature, the time is 20min, using 25%~28% ammonia (with NH3Meter) back extraction is carried out to extractant, temperature Spend for 40 DEG C, desorption time is 1h, the extractant after back extraction can with recycling, de- molybdenum process after filtrate, obtain sulphuric acid, The concentration of gained sulphuric acid is 9.92%.
Water logging in the present embodiment goes out molybdenum in product to be existed with molybdic acid hydrate form, is computed understanding, the oxygenation efficiency of molybdenum is 97.91%;It is 99.42% by the quality purity through ammonia leaching, filtration, the prepared ammonium molybdate product of crystallization processes for the filter cake;The present embodiment In by filtrate through extraction process be obtained ammonium molybdate product quality purity be 98.98%.In the present embodiment, the overall recovery of molybdenum is 95.47%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to the ammonium molybdate product obtaining, and again show that The ammonium molybdate arriving is in bar-shaped and favorable dispersibility, and structure is more complete.
Comparative example 1
This comparative example is differed only in embodiment 1, and in step (1), molybdenite powder and water press solid-to-liquid ratio 1:8 mixing, remove Outside this, remaining preparation process and condition select all same as Example 1.Water logging in the present embodiment goes out in product molybdenum to be hydrated Molybdic acid exists, and is computed understanding, the oxygenation efficiency of molybdenum is 63.54%;Molybdenum is obtained through ammonia leaching, filtration, crystallization processes by filter cake The quality purity of sour ammonium product is 96.29%;The matter of ammonium molybdate product is obtained through ion-exchange process by filtrate in the present embodiment Amount purity is 99.13%.In the present embodiment, the overall recovery of molybdenum is 59.71%, and the concentration of gained sulphuric acid is 5.15%.
Comparative example 2
This comparative example is differed only in embodiment 1, and in step (1), molybdenite powder and water press solid-to-liquid ratio 1:1 mixing, removes Outside this, remaining preparation process and condition select all same as Example 1.Because solid-to-liquid ratio is too high, reaction is led to carry out one section After time, ore pulp is changed into sticky pasty state it has to stopped reaction.It is computed understanding, the oxygenation efficiency of molybdenum is 8.12%;By filter cake Quality purity through ammonia leaching, filtration, the prepared ammonium molybdate product of crystallization processes is 98.23%;After reaction, liquid phase does not have substantially, therefore From liquid phase, do not extract molybdenum, nor calculate sulfuric acid concentration.
Thus, it will be seen that highly purified ammonium molybdate product can be obtained using the inventive method so that molybdenum in molybdenite Overall recovery reach more than 95%, even as high as more than 98%, and the sulphuric acid of higher concentration can be obtained simultaneously.
Applicant states, the present invention illustrates the process of the present invention by above-described embodiment, but the present invention not office It is limited to above-mentioned processing step, that is, do not mean that the present invention has to rely on above-mentioned processing step and could implement.Art Technical staff is it will be clearly understood that any improvement in the present invention, the equivalence replacement to raw material selected by the present invention and auxiliary element Interpolation, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. a kind of method of oxygen pressure water seaoning process molybdenite coproduction ammonium molybdate and sulphuric acid is it is characterised in that methods described includes Following steps:
(1) molybdenite powder is pressed 1 with water:2~1:7 solid-to-liquid ratio mix homogeneously, makes molybdenite ore pulp;
(2) the molybdenite ore pulp that step (1) obtains being injected pressure reaction still presses water logging anti-so as to carry out oxygen with oxidizing gas Should;
(3) slurry obtaining step (2) is filtered, and obtains filter cake and filtrate;
(4) filter cake that step (3) obtains is obtained ammonium molybdate product through ammonia leaching, filtration, crystallization;
(5), after step (3) gained filtrate being processed through de- molybdenum, obtain sulfuric acid product.
2. method according to claim 1 it is characterised in that in the described molybdenite powder of step (1) percent mass of molybdenum contain Measure as 25%~58%, preferably 45%~58%;
Preferably, granularity < 100 mesh of the described molybdenite powder of step (1), preferably < 250 mesh;
Preferably, the described solid-to-liquid ratio of step (1) is 1:3~1:6;
Preferably, the described oxidizing gas of step (2) be oxygen, in air or ozone any one or at least two mixing Thing, preferably oxygen;
Preferably, the described oxygen of step (2) presses the temperature of water logging reaction to be 180 DEG C~220 DEG C, preferably 200 DEG C~220 DEG C;
Preferably, the described oxygen of step (2) presses the oxygen partial pressure of water logging reaction is 0.5~2MPa, preferably 1~2MPa;
Preferably, the described oxygen of step (2) press water logging reaction time be 20min~4h, preferably 1~4h, further preferred 1~ 2h.
3. method according to claim 1 and 2 is it is characterised in that the Mo ion concentration in the described filtrate of step (3) is 0.1~80g/L;
Preferably, the H in the described filtrate of step (3)+Content is 0.1~10mol/L.
4. the method according to any one of claim 1-3 it is characterised in that step (4) described ammonia leaching before to step Suddenly the filter cake that (3) obtain is washed, and removes the attachment on filter cake surface, obtains washing liquid;
Preferably, described washing uses water as detergent.
5. method according to claim 4 it is characterised in that in described washing liquid Mo ion concentration be 0.01~20g/L;
Preferably, H in described washing liquid+Content is 0.01~4mol/L.
6. the method according to any one of claim 1-5 is it is characterised in that the described ammonia of step (4) soaks the leaching using Agent is with NH3Meter mass fraction is the ammonia of 20%-28%.
7. the method according to any one of claim 1-6 is it is characterised in that the method that processes of the described de- molybdenum of step (5) For ion exchange or extraction.
8. method according to claim 7 is it is characterised in that described ion exchange is to be entered using anion exchange resin Row ion exchange, the molybdate anion in filtrate is separated from filtrate;
Preferably, described anion exchange resin is amido class macroporous weakly basic anion exchange resin;
Preferably, during described ion exchange, anion exchange resin and the mass volume ratio of filtrate are 1:6~1:60, preferably 1:6 ~1:25;
Preferably, temperature during described ion exchange is 0~80 DEG C, preferably 20~60 DEG C;
Preferably, the time of described ion exchange is 10min~5h, preferably 30min~3h.
9. method according to claim 7 is it is characterised in that described extraction is using amine extractant, filtrate to be carried out Extraction, the molybdate anion in filtrate is extracted from filtrate;
Preferably, described amine extractant is three (the octyl- last of the ten Heavenly stems) alkyl tertiary amine;
Preferably, the temperature of described extraction is 0 DEG C~80 DEG C, preferably 20 DEG C~50 DEG C;
Preferably, the time of extraction is 10min~5h, preferably 1~2h.
10. the method according to any one of claim 1-9 is it is characterised in that the method comprising the steps of:
(1) molybdenite powder is pressed 1 with water:2~1:7 solid-to-liquid ratio mix homogeneously, makes molybdenite ore pulp;
(2) the molybdenite ore pulp obtaining step (1) injects pressure reaction still so as to oxidizing gas 180 DEG C~220 DEG C, carry out oxygen pressure water logging reaction 20min~4h under 0.5~2MPa;
(3) slurry obtaining step (2) is filtered, and obtains filter cake and filtrate;
(4) filter cake obtaining step (3) is washed, remove filter cake surface attachment, and after through ammonia leaching, filter, crystallization Prepared ammonium molybdate product;
(5) step (3) gained filtrate is carried out through ion exchange or extraction, after de- molybdenum process, obtain sulfuric acid product;
Described ion exchange is to utilize the mass volume ratio with filtrate to be 1:6~1:60 anion exchange resin is 0~80 Carry out ion exchange 10min~5h at DEG C, the molybdate anion in filtrate is separated from filtrate;Described extraction is At 0 DEG C~80 DEG C, filtrate is extracted using amine extractant, the molybdate anion in filtrate is extracted from filtrate Come.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN111560518A (en) * 2020-07-01 2020-08-21 长沙有色冶金设计研究院有限公司 Treatment method of copper-containing molybdenum concentrate
US11377365B2 (en) * 2018-10-30 2022-07-05 Molibdenos Y Metales S.A. Process for the selective removal of copper compounds and other impurities with respect to molybdenum and rhenium, from molybdenite concentrates

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CN1713943A (en) * 2001-05-09 2005-12-28 H.C.施塔克有限公司 Production of pure molybdenum oxide from low grade molybdenite concentrates

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN1713943A (en) * 2001-05-09 2005-12-28 H.C.施塔克有限公司 Production of pure molybdenum oxide from low grade molybdenite concentrates

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11377365B2 (en) * 2018-10-30 2022-07-05 Molibdenos Y Metales S.A. Process for the selective removal of copper compounds and other impurities with respect to molybdenum and rhenium, from molybdenite concentrates
CN111560518A (en) * 2020-07-01 2020-08-21 长沙有色冶金设计研究院有限公司 Treatment method of copper-containing molybdenum concentrate

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