CN106477630B - A kind of method of oxygen pressure water seaoning processing molybdenite coproduction ammonium molybdate and sulfuric acid - Google Patents
A kind of method of oxygen pressure water seaoning processing molybdenite coproduction ammonium molybdate and sulfuric acid Download PDFInfo
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Abstract
The present invention provides a kind of method of oxygen pressure water seaoning processing molybdenite coproduction ammonium molybdate and sulfuric acid, the described method comprises the following steps：Molybdenite powder and water are pressed 1:2~1:7 solid-to-liquid ratio is well mixed, and molybdenite ore pulp is made；Molybdenite ore pulp is injected into pressure reaction still, it is carried out oxygen pressure water logging reaction with oxidizing gas；Obtained slurry is filtered, obtains filter cake and filtrate；Filter cake is soaked through ammonia, filtered, crystallizes obtained ammonium molybdate product；Filtrate obtains sulfuric acid product after de- molybdenum processing.The method of the invention reaches more than 95% for the overall recovery of molybdenum, even as high as more than 98%, the sulfuric acid of higher concentration can be obtained simultaneously, and generation environment does not pollute, simply, efficiently, save, be it is a kind of it is environment-friendly efficiently using molybdenite come coproduction ammonium molybdate and the hydrometallurgy process for cleanly preparing of sulfuric acid, there is good industrial applications prospect.
Description
Technical field
The invention belongs to molybdenum chemical industry and field of hydrometallurgy, more particularly to a kind of oxygen pressure water seaoning processing molybdenite coproduction molybdenum
The method of sour ammonium and sulfuric acid.
Background technology
Molybdenite is the widest molybdenum ore of molybdenum industrial application, is the primary raw material for producing ammonium molybdate and molybdenum oxide.At present should
It is the technique for applying of ripe main flow with molybdenite oxidizing roasting-ammonia soaking technology production ammonium molybdate, but this technique can produce greatly
The SO of amount2Flue gas, caused SO the characteristics of due to equipment and technique itself2The most concentration of flue gas it is relatively low, it is impossible to reach and prepare sulphur
The requirement of acid, SO2Flue gas pollutes environment by outer row.
Wet-treating molybdenite technique can preferably solve SO2Fume emission problem, many scholars and enterprise have done greatly
Quantifier elimination, the main method of wet-treating molybdenite can be divided into electrochemical leaching method at present, acid oxidation leaches and alkaline process oxygen
Change and leach.
CN101775491A discloses a kind of electrolytic method using NaCl as medium, this electrochemical leaching method it is anti-
Although it is room temperature to answer temperature, and reaction medium is cheap and easy to get, and current efficiency is only capable of 60% or so.
The oxidant that acid oxidation leaches can be oxidizing gas or liquid oxidizer, this kind of processing brightness molybdenum
The method of ore deposit, such as the method disclosed in CN104745812A, using sulfuric acid as medium, nitric acid or oxygen are as oxidant, instead
Answer the acidity of system very big, more strict is required to the material of consersion unit.
The method of alkaline process oxidation processes molybdenite uses sodium hydroxide as reaction medium more, such as CN102534207A and
The method of alkaline process oxidation processes molybdenite disclosed in CN101956070A, although avoiding lacking for concentrated acid severe corrosion equipment
Point, also without SO2Smoke pollution environment, but during the course of the reaction alkali except with molybdenite molybdenum reaction will also with molybdenite
Reaction of Salmon-Saxl, and be twice with the alkali consumption of molybdenum reaction with the alkali consumption of reaction of Salmon-Saxl, produce a large amount of cheap accessory substances,
It is serious to consume alkali so that the economy of this method substantially reduces, and constrains the commercial applications of oxygen pressure alkaline leaching.
In addition, somebody proposes to use medium of the water as oxygen leaching, 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 obtained after leaching produces work after processing
Industry molybdenum trioxide, obtained liquid phase use NaHS after the pH for adjusting leachate is 7~8, to remove precipitation as impurity removal reagents
Impurity out.Because acidity is stronger in the liquid phase after water logging, pH is adjusted using NaHS, the method for removal of impurities can consume largely
NaHS, also result in water logging generation sulfuric acid be neutralized into sodium sulfate byproduct, cause in reclaim liquid phase it is valuable into
The cost divided is too high.
Therefore, it is expected to develop a kind of coproduction ammonium molybdate and sulphur environment-friendly, resource utilization is high, flow is short in this area
The method of acid.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of oxygen pressure water seaoning processing molybdenite coproduction molybdenum
The method of sour ammonium and sulfuric acid.
To reach this goal of the invention, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of method of oxygen pressure water seaoning processing molybdenite coproduction ammonium molybdate and sulfuric acid, described
Method comprises the following steps：
(1) molybdenite powder and water are pressed 1:2~1:8 solid-to-liquid ratio is well mixed, and molybdenite ore pulp is made；
(2) the molybdenite ore pulp for obtaining step (1) injects pressure reaction still, it is carried out oxygen pressure water with oxidizing gas
Leaching reaction；
(3) slurry that step (2) obtains is filtered, obtains filter cake and filtrate；
(4) filter cake that step (3) obtains soaked through ammonia, filtered, crystallizing obtained ammonium molybdate product；
(5) filtrate obtained by step (3) is obtained into sulfuric acid product after de- molybdenum processing.
The present invention is by the way that the solid-to-liquid ratio of molybdenite powder and water is controlled in the larger context, i.e., and 1:2~1:7, so as to reach
To faster reaction speed and the oxygenation efficiency of higher molybdenum, this and conventional wet-leaching molybdenite (acid system or alkaline process) method
In the cognition that is favorably improved speed of low solid-to-liquid ratio have difference substantially because water logging process is the process of production acid, necessarily
The acid of concentration is favorably improved solubility of the oxygen in leachate, so as to reach the effect for improving reaction rate, but in the past
The extraction of water seaoning molybdenum when, not conscious this point, the solid-to-liquid ratio used is and similar low solid of common acid system and alkaline process
Liquor ratio, this not only reduces reaction rate, can also increase the molybdenum content in liquid phase, reduces the yield of reaction, also add reaction
Inventory and add energy consumption, improve production cost.Present invention contemplates that faster reaction speed is obtained, the higher sulphur of concentration
Acid, thus add too many water and can reduce the concentration of sulfuric acid, and the market price of dilute sulfuric acid is relatively low, it is higher in order to generate concentration
Sulfuric acid, it is desirable to which, using less water volume during oxygen pressure water logging, the present invention is by the molybdenite suitable for preparation method of the present invention
It is 1 that the solid-to-liquid ratio of powder and water, which is screened to obtain in solid-to-liquid ratio,: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, can both widen using brightness
The grade scope of molybdenum ore, the recovery rate for ensureing molybdenum, the sulfuric acid of higher concentration can be obtained again.
Preferably, in step (1) the molybdenite powder molybdenum weight/mass percentage composition be 25%~58%, such as 25%,
27%th, 29%, 31%, 33%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 54%, 56% or 58%,
Preferably 45%~58%, the present invention has widened the grade scope using molybdenite.
Preferably, the mesh of granularity ＜ 100 of step (1) the molybdenite powder, such as the 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., the preferably mesh of ＜ 250.
Preferably, step (1) described solid-to-liquid ratio is 1:2~1:6, solid-to-liquid ratio is controlled 1 in the present invention:2~1:6
When, it can make it that the concentration for the sulfuric acid that the organic efficiency of molybdenum is higher, is obtained in addition under the solid-to-liquid ratio is also higher.In the present invention
The solid-to-liquid ratio refers to the ratio between the quality (g) of solid and the volume (mL) of liquid.
Preferably, step (2) described oxidizing gas is any one in oxygen, air or ozone or at least two
Mixture, preferably oxygen.
Preferably, the temperature of step (2) oxygen pressure water logging reaction is 180 DEG C~220 DEG C, for example, 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 oxygen partial pressure of step (2) oxygen pressure 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.In the present invention if oxygen partial pressure is relatively low, then it can make it that the speed of reaction is slower, be unfavorable for producing；If oxygen point
Pressure is higher, although reaction speed can be improved, adds the cost of high withstand voltage equipment, therefore can control oxygen partial pressure
In the scope of the present invention, and during preferably 1~2MPa can balanced reaction speed and Cost Problems, 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, so as to improve production efficiency.
Preferably, the time of step (2) oxygen pressure water logging reaction is 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,
Preferably 1~4h, further preferred 1~2h.The present invention will control within the above range in the reaction time, it is ensured that oxygen presses water logging
The leaching rate of reaction is more than 95%.
Can cause by the pressure water logging reaction of step (2) oxygen in the present invention the oxygenation efficiency of molybdenite 95% with
On, such as 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98% or 99%.
Preferably, the Mo ion concentrations in step (3) described filtrate are 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 step (3) described filtrate+Content is 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 obtained before step (4) the ammonia leaching to step (3) washs, and removes filter cake surface
Attachment, obtain washing lotion.Preferably, the washing uses water as detergent.
Preferably, the washing lotion can return to the recycling of molybdenite ore pulp preparation process as needed.
Preferably, Mo ion concentrations are 0.01~20g/L in the washing lotion, for example, 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 the washing lotion+Content is 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 the filtrate and washing lotion is deposited in the form of the molybdate anion of complexity
Be advantageous to subsequent technique and molybdenum ion is extracted from liquid phase.
Preferably, the leaching agent that step (4) the ammonia leaching uses is with NH3Count ammonia of the mass fraction 20%~28%
Water, such as the mass fraction of ammoniacal liquor is 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27% or 28%.
Preferably, the method for step (5) the de- molybdenum processing is ion-exchange or extraction.It is described in the present invention de-
The molybdate anion that molybdenum refers to the process of in filtrate to contain is got rid of.
Preferably, the ion-exchange is to carry out ion exchange using anion exchange resin, it is therefore an objective to by filtrate
Molybdate anion separated from filtrate.
Preferably, the anion exchange resin is amido class macroporous weakly basic anion exchange resin, for example, D314 or
D301 etc..
Preferably, anion exchange resin and the mass volume ratio of filtrate are 1 during the ion exchange:6~1:60, such as
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, the temperature during 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, preferably 70 DEG C or 80 DEG C, 20~60 DEG C.
Preferably, the time of the ion exchange is 10min~5h, for example, 10min, 20min, 30min, 40min,
50min, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, preferably 30min~3h.
Preferably, the extraction is extracts using amine extractant to filtrate, by molybdate the moon in filtrate from
Son extracts from filtrate.
Preferably, the amine extractant is three (the octyl- last of the ten Heavenly stems) alkyl tertiary amines.
Regulator can be added as needed in extraction process, such as add sec-octyl alcohol and kerosene as regulator, it is right
Molybdenum acid ion in filtrate is extracted.
Preferably, the temperature of the 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 extract molybdenum in solution using ion-exchange or extraction from filtrate, has selectively good excellent
Gesture, while removing molybdenum in liquid phase, the molybdenum extracted can be produced into high purity product ammonium molybdate.In addition the process it is simple,
Efficiently, save, overcome and must first be cleaned using the molybdenum in Traditional Method recovery leachate, reuse evaporative crystallization method recovery molybdenum,
High energy consumption, efficiency are low and the shortcomings that process is numerous and diverse.
As the preferred technical solution of the present invention, oxygen pressure water seaoning processing molybdenite coproduction ammonium molybdate and sulphur of the present invention
The method of acid specifically includes following steps：
(1) molybdenite powder and water are pressed 1:2~1:7 solid-to-liquid ratio is well mixed, and molybdenite ore pulp is made；
(2) the molybdenite ore pulp obtained step (1) injects pressure reaction still, make its with oxidizing gas 180 DEG C~
220 DEG C, oxygen pressure water logging reaction 20min~4h is carried out under 0.5~2MPa；
(3) slurry that step (2) obtains is filtered, obtains filter cake and filtrate；
(4) filter cake that step (3) obtains is washed, removes the attachment on filter cake surface, and after soak, filter through ammonia,
Ammonium molybdate product is made in crystallization；
(5) filtrate obtained by step (3) is obtained into sulfuric acid product after ion-exchange or extraction carry out de- molybdenum processing；
The ion-exchange is that to utilize with the mass volume ratio of filtrate be 1:6~1:60 anion exchange resin is 0
Ion exchange 10min~5h is carried out at~80 DEG C, the molybdate anion in filtrate is separated from filtrate；The extraction
Method is extracted the molybdate anion in filtrate to be extracted using amine extractant at 0 DEG C~80 DEG C to filtrate from filtrate
Take out.
The present invention be it is a kind of it is environment-friendly efficiently using molybdenite come the cleaning of the hydrometallurgy of coproduction ammonium molybdate and sulfuric acid
Production technology, there is good industrial applications prospect.
Compared with prior art, the invention has the advantages that：
(1) present invention reduces extent of corrosion of the concentrated acid medium to equipment, also causes operating environment using water as medium
Well.
(2) present invention handles molybdenite by the way of pressure oxidation water logging, and water logging, more than 90% brightness molybdenum are pressed through peroxide
Ore deposit is changed into molybdic acid hydrate and is transferred to solid phase, comprises only the hydrate of molybdic acid in solid phase in addition to containing a small amount of silica,
Ammonia soaking technology can directly be continued to use and prepare ammonium molybdate product.Copper, iron, lead and other elements in molybdenite are transferred to liquid with cationic form
Phase, without being mixed into solid phase with molybdic acid hydrate in the form of molybdate, method of the invention can obtain the molybdic acid of high-purity
Ammonium product so that the overall recovery of molybdenum reaches more than 95%, even as high as more than 98% in molybdenite.
(3) present invention avoids SO using hydrometallurgy cleaning procedure processing molybdenite2The discharge of flue gas, eliminates cigarette
Pollution of the gas to environment.
(4) present invention is reclaimed the molybdenum ion in water-leach liquor using ion-exchange or extraction, and flow is short, efficiency
Height, and without being adjusted to the pH value of filtrate during ion exchange or extraction.
(5) present invention not only makes full use of the Mo resource in molybdenite, and the Sulphur ressource in molybdenite also is changed into sulphur
Acid, the high-efficiency cleaning for realizing molybdenite resource utilize.
Brief description of the drawings
Fig. 1 is the process flow diagram that the present invention presses water seaoning processing molybdenite coproduction ammonium molybdate and sulfuric acid using oxygen.
Fig. 2 is ESEM (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.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Embodiment 1
In the present embodiment, processing molybdenite coproduction ammonium molybdate and sulfuric acid are prepared by the following method, is specifically included following
Step (its schematic flow sheet is as shown in Figure 1)：
(1) solid-to-liquid ratio 1 will be pressed with water less than molybdenite powder of 250 purposes containing molybdenum 45%:2(g:ML) it is well mixed, is made
Molybdenite ore pulp；
(2) molybdenite is starched into injection pressure reaction still, at a temperature of 200 DEG C, entered with partial pressure for 1MPa oxidizing gas
Row oxygen pressure water logging reaction 1.5h；
(3) slurry that step (2) obtains is filtered, obtains filter cake and filtrate；
(4) filter cake that step (3) obtains soaked through ammonia, filtered, crystallizing obtained ammonium molybdate product；
(5) filtrate obtained by step (3) is subjected to de- molybdenum processing, filtrate need not adjust pH value, be handed over using weakly-basic anion
Change resin D301 and carry out anion exchange reaction, the solid-to-liquid ratio of D301 and filtrate is 1:15(g:ML), 40 DEG C of temperature, time are
120min, using 25%~28% ammoniacal liquor (with NH3Meter) resin is desorbed (regeneration), temperature is 40 DEG C, and desorption time is
1h, desorption obtain pure ammonium molybdate solution, and the resin after desorption after molybdenum processing is taken off to filtrate, can be obtained with recycling
Sulfuric acid, the concentration of gained sulfuric acid is 23.88%.
Water logging in the present embodiment goes out molybdenum in product to be existed in the form of molybdic acid hydrate, is computed understanding, the oxygenation efficiency of molybdenum is
98.86%；Soaked, filtered through ammonia by filter cake in the present embodiment, the quality purity of the obtained ammonium molybdate product of crystallization processes is
99.13%；The quality purity that ammonium molybdate product is made through ion-exchange process by filtrate in the present embodiment is 99.30%.This reality
The overall recovery for applying molybdenum in example is 98.24%.
The ammonium molybdate product that the present embodiment is prepared using ESEM (JSM-7610F, JEOL) is characterized,
As a result as shown in Fig. 2 the ammonium molybdate as can be seen from the figure prepared is in bar-shaped and favorable dispersibility.
The ammonium molybdate product that embodiment is prepared using X-ray diffractometer (Phillips PW 223/30) is carried out
Characterize, as a result as shown in figure 3, as can be seen from the figure the structure of ammonium molybdate is more complete.
Embodiment 2
In the present embodiment, processing molybdenite coproduction ammonium molybdate and sulfuric acid are prepared by the following method, is specifically included following
Step (its schematic flow sheet is as shown in Figure 1)：
(1) solid-to-liquid ratio 1 will be pressed with water less than molybdenite powder of 250 mesh containing molybdenum 58%:7(g:ML) it is well mixed, brightness is made
Molybdenum ore ore pulp；
(2) molybdenite is starched into injection pressure reaction still, at a temperature of 180 DEG C, with the oxidizing gas that partial pressure is 1.5MPa
Carry out oxygen pressure water logging reaction 4h；
(3) slurry that step (2) obtains is filtered, obtains filter cake and filtrate；
(4) filter cake that step (3) obtains soaks through ammonia, filtered, crystallizing obtained ammonium molybdate product；
(5) filtrate obtained by step (3) is subjected to de- molybdenum processing, filtrate need not adjust pH value, be handed over using weakly-basic anion
Change resin D301 and carry out anion exchange reaction, the solid-to-liquid ratio of D301 and filtrate is 1:6(g:ML), 40 DEG C of temperature, time are
50min, using 25%~28% ammoniacal liquor (with NH3Meter) resin is desorbed (regeneration), temperature is 40 DEG C, and desorption time is
1h, the resin after desorption after molybdenum processing is taken off to filtrate, can obtain sulfuric acid, the concentration of gained sulfuric acid is with recycling
10.32%.
Water logging in the present embodiment goes out molybdenum in product to be existed in the form of molybdic acid hydrate, is computed understanding, the oxygenation efficiency of molybdenum is
97.91%；Soaked, filtered through ammonia by filter cake, the quality purity of the obtained ammonium molybdate product of crystallization processes is 99.42%；The present embodiment
In by filtrate through ion-exchange process be made 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 obtained ammonium molybdate product, are again showed that
The ammonium molybdate arrived is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 3
In the present embodiment, processing molybdenite coproduction ammonium molybdate and sulfuric acid are prepared by the following method, is specifically included following
Step (its schematic flow sheet is as shown in Figure 1)：
(1) solid-to-liquid ratio 1 will be pressed with water less than molybdenite powder of 100 mesh containing molybdenum 47%:6(g:ML) it is well mixed, brightness is made
Molybdenum ore ore pulp；
(2) molybdenite slurry liquid is injected into pressure reaction still, at a temperature of 220 DEG C, with the oxidisability that partial pressure is 0.5MPa
Gas carries out oxygen pressure water logging reaction 2h；
(3) slurry obtained by above-mentioned second step is filtered, obtains filter cake and filtrate；
(4) filter cake after washing such as soaks, filtered, crystallizing at the obtained ammonium molybdate product through ammonia；
(5) filtrate obtained by above-mentioned 3rd step is subjected to de- molybdenum processing, filtrate need not adjust filtrate pH value, use weak base
Property anion exchange resin D301 carry out anion exchange reaction, solid-to-liquid ratio 1:6(g:ML), 30 DEG C of temperature, time 2h, make
With 25%~28% ammoniacal liquor (with NH3Meter) resin is desorbed (regeneration), temperature is 40 DEG C, desorption time 1h, after desorption
Resin sulfuric acid after molybdenum processing is taken off to filtrate, can be obtained with recycling, the concentration of gained sulfuric acid is 9.75%.
Water logging in the present embodiment goes out molybdenum in product to be existed in the form of molybdic acid hydrate, is computed understanding, the oxygenation efficiency of molybdenum is
95.79%；It is 99.52% the technique such as to soak, filter, crystallize through ammonia by filter cake the quality purity of ammonium molybdate product is made；By filtrate
The quality purity that ammonium molybdate product is made through techniques such as ion exchanges is 99.79%, and the overall recovery of molybdenum is in the present embodiment
96.01%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to obtained ammonium molybdate product, are again showed that
The ammonium molybdate arrived is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 4
In the present embodiment, processing molybdenite coproduction ammonium molybdate and sulfuric acid are prepared by the following method, is specifically included following
Step (its schematic flow sheet is as shown in Figure 1)：
(1) solid-to-liquid ratio 1 will be pressed less than 54% molybdenite powder of 250 mesh and water:2(g:ML) it is well mixed, molybdenite is made
Ore pulp；
(2) molybdenum concntrate ore pulp feed liquid is injected into pressure reaction still, at a temperature of 180 DEG C, with the oxidisability that partial pressure is 2MPa
Gas carries out oxygen pressure water logging reaction 180min；
(3) slurry obtained by above-mentioned second step is filtered, obtains filter cake and filtrate；
(4) filter cake after washing such as soaks, filtered, crystallizing at the obtained ammonium molybdate product through ammonia；
(5) filtrate obtained by above-mentioned 3rd step is subjected to de- molybdenum processing, filtrate need not adjust filtrate pH value, use weak base
Property anion exchange resin D301 carry out anion exchange reaction, solid-to-liquid ratio 1:6(g:ML), 40 DEG C of temperature, time are
50min, using 25%~28% ammoniacal liquor (with NH3Meter) resin is desorbed (regeneration), temperature is 40 DEG C, and desorption time is
1h, the resin after desorption after molybdenum processing is taken off to filtrate, can obtain sulfuric acid, the concentration of gained sulfuric acid is with recycling
25.12%.
Water logging in the present embodiment goes out molybdenum in product to be existed in the form of molybdic acid hydrate, is computed understanding, the oxygenation efficiency of molybdenum is
96.17%；Soaked, filtered through ammonia by filter cake in the present embodiment, the quality purity of the obtained ammonium molybdate product of crystallization processes is
99.48%；The quality purity that ammonium molybdate product is made through ion-exchange process by filtrate in the present embodiment is 99.88%.This reality
The overall recovery for applying molybdenum in example is 97.59%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to obtained ammonium molybdate product, are again showed that
The ammonium molybdate arrived is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 5
In the present embodiment, processing molybdenite coproduction ammonium molybdate and sulfuric acid are prepared by the following method, is specifically included following
Step (its schematic flow sheet is as shown in Figure 1)：
(1) solid-to-liquid ratio 1 will be pressed less than 56% molybdenite powder of 250 mesh and water:5(g:ML) it is well mixed, molybdenite is made
Ore pulp；
(2) molybdenum concntrate ore pulp feed liquid is injected into pressure reaction still, at a temperature of 220 DEG C, with the oxidisability that partial pressure is 2MPa
Gas carries out oxygen pressure water logging reaction 60min；
(3) slurry obtained by above-mentioned second step is filtered, obtains filter cake and filtrate；
(4) filter cake after washing such as soaks, filtered, crystallizing at the obtained ammonium molybdate product through ammonia；
(5) filtrate obtained by above-mentioned 3rd step is subjected to de- molybdenum processing, filtrate need not adjust filtrate pH value, use weak base
Property anion exchange resin D301 carry out anion exchange reaction, solid-to-liquid ratio 1:6(g:ML), 40 DEG C of temperature, time are
50min, using 25%~28% ammoniacal liquor (with NH3Meter) resin is desorbed (regeneration), temperature is 40 DEG C, and desorption time is
1h, the resin after desorption after molybdenum processing is taken off to filtrate, can obtain sulfuric acid, the concentration of gained sulfuric acid is with recycling
11.67%.
Water logging in the present embodiment goes out molybdenum in product to be existed in the form of molybdic acid hydrate, is computed understanding, the oxygenation efficiency of molybdenum is
99.91%；Soaked, filtered through ammonia by filter cake in the present embodiment, the quality purity of the obtained ammonium molybdate product of crystallization processes is
99.15%；The quality purity that ammonium molybdate product is made through ion-exchange process by filtrate in the present embodiment is 99.87%.This reality
The overall recovery for applying molybdenum in example is 99.47%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to obtained ammonium molybdate product, are again showed that
The ammonium molybdate arrived 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 with water by solid-to-liquid ratio 1:4 mixing, are removed
Outside this, remaining preparation process selects same as Example 2 with condition.Water logging in the present embodiment goes out in product molybdenum to be hydrated
Molybdic acid is present, and is computed understanding, the oxygenation efficiency of molybdenum is 99.64%；Soaked, filtered through ammonia by filter cake, molybdenum is made in crystallization processes
The quality purity of sour ammonium product is 99.59%；The matter of ammonium molybdate product is made in the present embodiment through ion-exchange process by filtrate
It is 99.81% to measure purity.The overall recovery of molybdenum is 98.43% in the present embodiment, and the concentration of gained sulfuric acid is 18.28%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to obtained ammonium molybdate product, are again showed that
The ammonium molybdate arrived is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 7
The grade (i.e. molybdenum content) for differing only in molybdenite powder in step (1) of the present embodiment and embodiment 2 is 25%,
In addition, remaining preparation process selects same as Example 2 with condition.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%；Soaked, filtered through ammonia by filter cake, crystallization processes are made
The quality purity of ammonium molybdate product is 99.10%；Ammonium molybdate product is made through ion-exchange process by filtrate in the present embodiment
Quality purity is 99.72%.The overall recovery of molybdenum is 97.93% in the present embodiment, and the concentration of gained sulfuric acid is 14.23%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to obtained ammonium molybdate product, are again showed that
The ammonium molybdate arrived is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 8
The grade (i.e. molybdenum content) for differing only in molybdenite powder in step (1) of the present embodiment and embodiment 2 is 30%,
In addition, remaining preparation process selects same as Example 2 with condition.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%；Soaked, filtered through ammonia by filter cake, crystallization processes are made
The quality purity of ammonium molybdate product is 99.15%；Ammonium molybdate product is made through ion-exchange process by filtrate in the present embodiment
Quality purity is 99.37%.The overall recovery of molybdenum is 97.55% in the present embodiment, and the concentration of gained sulfuric acid is 17.48%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to obtained ammonium molybdate product, are again showed that
The ammonium molybdate arrived is in bar-shaped and favorable dispersibility, and structure is more complete.
Embodiment 9
The present embodiment and the step (5) that differs only in of embodiment 2 are made using 20% 3 (the octyl- last of the ten Heavenly stems) alkyl tertiary amine (N235)
For extractant, de- molybdenum processing is carried out to filtrate using the kerosene of 10% sec-octyl alcohol+70% as regulator, extractant is with leaching filtrate body
Product is than being 1:5,40 DEG C, time 20min of temperature, using 25%~28% ammoniacal liquor (with NH3Meter) extractant is stripped, temperature
To spend for 40 DEG C, desorption time 1h, the extractant after back extraction can be taken off the filtrate after molybdenum processing, obtained sulfuric acid with recycling,
The concentration of gained sulfuric acid is 9.92%.
Water logging in the present embodiment goes out molybdenum in product to be existed in the form of molybdic acid hydrate, is computed understanding, the oxygenation efficiency of molybdenum is
97.91%；Soaked, filtered through ammonia by filter cake, the quality purity of the obtained ammonium molybdate product of crystallization processes is 99.42%；The present embodiment
In by filtrate through extraction process be made ammonium molybdate product quality purity be 98.98%.The overall recovery of molybdenum is in the present embodiment
95.47%.
Same application scanning Electronic Speculum and X-ray diffractometer are characterized to obtained ammonium molybdate product, are again showed that
The ammonium molybdate arrived is in bar-shaped and favorable dispersibility, and structure is more complete.
Comparative example 1
The comparative example differs only in embodiment 1, and molybdenite powder presses solid-to-liquid ratio 1 with water in step (1):8 mixing, are removed
Outside this, remaining preparation process selects same as Example 1 with condition.Water logging in the present embodiment goes out in product molybdenum to be hydrated
Molybdic acid is present, and is computed understanding, the oxygenation efficiency of molybdenum is 63.54%；Soaked, filtered through ammonia by filter cake, molybdenum is made in crystallization processes
The quality purity of sour ammonium product is 96.29%；The matter of ammonium molybdate product is made in the present embodiment through ion-exchange process by filtrate
It is 99.13% to measure purity.The overall recovery of molybdenum is 59.71% in the present embodiment, and the concentration of gained sulfuric acid is 5.15%.
Comparative example 2
The comparative example differs only in embodiment 1, and molybdenite powder presses solid-to-liquid ratio 1 with water in step (1):1 mixing, is removed
Outside this, remaining preparation process selects same as Example 1 with condition.Because solid-to-liquid ratio is too high, reaction is caused 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
Soak, filter through ammonia, the quality purity of the obtained ammonium molybdate product of crystallization processes is 98.23%；There is no liquid phase, therefore substantially after reaction
Molybdenum is not extracted from liquid phase, sulfuric acid concentration can not be calculated.
Thus, it will be seen that the ammonium molybdate product of high-purity 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 sulfuric acid of higher concentration can be obtained simultaneously.
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (30)
1. a kind of method of oxygen pressure water seaoning processing molybdenite coproduction ammonium molybdate and sulfuric acid, it is characterised in that methods described includes
Following steps：
(1) molybdenite powder and water are pressed 1:2~1:7 solid-to-liquid ratio is well mixed, and molybdenite ore pulp is made；
(2) the molybdenite ore pulp for obtaining step (1) injects pressure reaction still, it is carried out oxygen with oxidizing gas and presses water logging anti-
Should；
(3) slurry that step (2) obtains is filtered, obtains filter cake and filtrate；
(4) filter cake that step (3) obtains soaked through ammonia, filtered, crystallizing obtained ammonium molybdate product；
(5) filtrate obtained by step (3) is obtained into sulfuric acid product after de- molybdenum processing；
The method of step (5) the de- molybdenum processing is ion-exchange or extraction, and the ion-exchange is to utilize anion
Exchanger resin carries out ion exchange, and the molybdate anion in filtrate is separated from filtrate, cloudy during the ion exchange
Ion exchange resin and the mass volume ratio of filtrate are 1:6~1:60, the temperature during ion exchange is 0~80 DEG C, described
The time of ion exchange is 10min~5；The extraction is extracts using amine extractant to filtrate, by filtrate
Molybdate anion extracts from filtrate, and the temperature of the extraction is 0 DEG C~80 DEG C, and the time of extraction is 10min~5h.
2. according to the method for claim 1, it is characterised in that the quality percentage of molybdenum contains in step (1) the molybdenite powder
Measure as 25%~58%.
3. according to the method for claim 2, it is characterised in that the quality percentage of molybdenum contains in step (1) the molybdenite powder
Measure as 45%~58%.
4. according to the method for claim 1, it is characterised in that the mesh of granularity ＜ 100 of step (1) the molybdenite powder.
5. according to the method for claim 4, it is characterised in that the mesh of granularity ＜ 250 of step (1) the molybdenite powder.
6. according to the method for claim 1, it is characterised in that step (1) described solid-to-liquid ratio is 1:3~1:6.
7. according to the method for claim 1, it is characterised in that step (2) described oxidizing gas is oxygen, air or smelly
In oxygen any one or at least two mixture.
8. according to the method for claim 7, it is characterised in that step (2) described oxidizing gas is oxygen.
9. according to the method for claim 1, it is characterised in that the temperature of step (2) the oxygen pressure water logging reaction is 180 DEG C
~220 DEG C.
10. according to the method for claim 9, it is characterised in that the temperature of step (2) the oxygen pressure water logging reaction is 200
DEG C~220 DEG C.
11. according to the method for claim 1, it is characterised in that the oxygen partial pressure of step (2) oxygen pressure water logging reaction is
0.5~2MPa.
12. according to the method for claim 11, it is characterised in that the oxygen partial pressure of step (2) the oxygen pressure water logging reaction
For 1~2MPa.
13. according to the method for claim 1, it is characterised in that the time of step (2) oxygen pressure water logging reaction is
20min~4h.
14. according to the method for claim 13, it is characterised in that the time of step (2) oxygen pressure water logging reaction for 1~
4h。
15. according to the method for claim 14, it is characterised in that the time of step (2) oxygen pressure water logging reaction for 1~
2h。
16. according to the method for claim 1, it is characterised in that the Mo ion concentrations in step (3) described filtrate are 0.1
~80g/L.
17. according to the method for claim 1, it is characterised in that the H in step (3) described filtrate+Content be 0.1~
10mol/L。
18. according to the method for claim 1, it is characterised in that step (3) is obtained before step (4) the ammonia leaching
Filter cake washed, remove the attachment on filter cake surface, obtain washing lotion.
19. according to the method for claim 18, it is characterised in that the washing uses water as detergent.
20. according to the method for claim 18, it is characterised in that Mo ion concentrations are 0.01~20g/L in the washing lotion.
21. according to the method for claim 18, it is characterised in that H in the washing lotion+Content is 0.01~4mol/L.
22. according to the method for claim 1, it is characterised in that the leaching agent that step (4) the ammonia leaching uses is with NH3Meter
Mass fraction is 20%-28% ammoniacal liquor.
23. according to the method for claim 1, it is characterised in that the anion exchange resin is amido class macropore weak base
Property anion exchange resin.
24. according to the method for claim 1, it is characterised in that anion exchange resin and filtrate during the ion exchange
Mass volume ratio be 1:6~1:25.
25. according to the method for claim 1, it is characterised in that the temperature during ion exchange is 20~60 DEG C.
26. according to the method for claim 1, it is characterised in that the time of the ion exchange is 30min~3h.
27. according to the method for claim 1, it is characterised in that the amine extractant is three (the octyl- last of the ten Heavenly stems) alkyl tertiary amines.
28. according to the method for claim 1, it is characterised in that the temperature of the extraction is 20 DEG C~50 DEG C.
29. according to the method for claim 1, it is characterised in that the time of the extraction is 1~2h.
30. according to the method for claim 1, it is characterised in that the described method comprises the following steps：
(1) molybdenite powder and water are pressed 1:2~1:7 solid-to-liquid ratio is well mixed, and molybdenite ore pulp is made；
(2) the molybdenite ore pulp for obtaining step (1) injects pressure reaction still, makes it with oxidizing gas 180 DEG C~220
DEG C, oxygen pressure water logging reaction 20min~4h is carried out under 0.5~2MPa；
(3) slurry that step (2) obtains is filtered, obtains filter cake and filtrate；
(4) filter cake that step (3) obtains is washed, removes the attachment on filter cake surface, and after soaked through ammonia, filter, crystallize
Ammonium molybdate product is made；
(5) filtrate obtained by step (3) is obtained into sulfuric acid product after ion-exchange or extraction carry out de- molybdenum processing；
The ion-exchange is that to utilize with the mass volume ratio of filtrate be 1:6~1:60 anion exchange resin is 0~80
Ion exchange 10min~5h is carried out at DEG C, the molybdate anion in filtrate is separated from filtrate；The extraction is
Filtrate is extracted at 0 DEG C~80 DEG C using amine extractant, the molybdate anion in filtrate is extracted from filtrate
Come.
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