CN115650293A - Ammonium molybdate production method - Google Patents
Ammonium molybdate production method Download PDFInfo
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- CN115650293A CN115650293A CN202211171590.5A CN202211171590A CN115650293A CN 115650293 A CN115650293 A CN 115650293A CN 202211171590 A CN202211171590 A CN 202211171590A CN 115650293 A CN115650293 A CN 115650293A
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 title claims abstract description 72
- 229940010552 ammonium molybdate Drugs 0.000 title claims abstract description 71
- 235000018660 ammonium molybdate Nutrition 0.000 title claims abstract description 71
- 239000011609 ammonium molybdate Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000002253 acid Substances 0.000 claims abstract description 69
- 238000002386 leaching Methods 0.000 claims abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 57
- 238000005554 pickling Methods 0.000 claims abstract description 57
- 238000005406 washing Methods 0.000 claims abstract description 53
- 238000003916 acid precipitation Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 39
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012452 mother liquor Substances 0.000 claims abstract description 36
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 33
- 239000011733 molybdenum Substances 0.000 claims abstract description 33
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 25
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012065 filter cake Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 5
- 239000003957 anion exchange resin Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 54
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 14
- 239000012535 impurity Substances 0.000 description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 10
- 238000007654 immersion Methods 0.000 description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of ammonium molybdate preparation, in particular to an ammonium molybdate production method, which comprises the following steps: s1: carrying out acid washing operation on solid industrial molybdenum oxide, and carrying out solid-liquid separation after the acid washing operation to obtain acid washing liquid and a filter cake; s2: recovering molybdenum in the pickling solution, and treating the filter cake by an ammonia leaching process to obtain ammonia leaching solution and ammonia leaching residue; s3: and (3) performing acid precipitation treatment on the ammonia leaching solution obtained in the step (S2) to obtain ammonium molybdate and acid precipitation mother liquor, and returning the acid precipitation mother liquor to the acid washing operation for reuse. The production method of ammonium molybdate can greatly improve the pickling effect and finally improve the yield of ammonium molybdate.
Description
Technical Field
The invention relates to the technical field of ammonium molybdate preparation, in particular to a production method of ammonium molybdate.
Background
Ammonium molybdate (NH) 4 ) 2 MoO 4 Is an important molybdate and is one of the most important molybdenum compounds. The method is mainly used for producing molybdenum catalysts, molybdenum powder and molybdenum metal products, and also can be used for producing chemical reagents, corrosion inhibitors, pigments, metal surface treatment agents, trace element fertilizers and the like, and the application range is still continuously expanded. Because the molybdenum metal products and most molybdenum chemical products use ammonium molybdate as precursors, the preparation process of ammonium molybdate directly influences the physicochemical property and the processing property of subsequent products and the cost factors related to the quality of the process.
At present, the ammonium molybdate produced by industrial oxides in China is mainly prepared by a classical method, the main process of the ammonium molybdate is acid pickling, and the current common acid pickling process is generally to carry out acid pickling operation on industrial molybdenum oxide by using mixed solution of ammonium nitrate and nitric acid in a normal pressure reaction kettle. The pickling solution is prepared by adding a proper amount of nitric acid into acid precipitation mother liquor, wherein the solid-liquid mass ratio is 1:3-1:4, the pH value in the pickling process is kept at 1-1.5, the pickling time is 1-1.5 h, and the temperature is controlled at 90-95 ℃, so that impurities in industrial molybdenum oxide, such as Na, K, cu, pb, fe, mg and the like, are washed away by using the nitric acid, and part of low-valence insoluble molybdate in the molybdenum trioxide is converted into molybdic acid.
The acid washing operation process plays an important role as a key link in the whole production process of ammonium molybdate, the main purpose of the acid washing operation process is to remove alkali metals (K, na and the like) and alkaline earth metals (Mg, ga and the like) in molybdenum trioxide so as to ensure the quality requirement of the ammonium molybdate, in the acid washing process, calcium, iron, copper, zinc and the like enter a liquid phase in the form of soluble salt, molybdenum trioxide is decomposed into acid-insoluble molybdic acid, and various impurities entering the liquid phase are effectively removed in the solid-liquid separation process. The pickling process directly determines the quality of an ammonium molybdate product, and the biggest influence is whether the recovery rate of molybdenum in the subsequent production process is effectively improved, while the method adopting normal-pressure pickling in the prior art has simple process and strong operability, but the conventional pretreatment method has some defects and deficiencies in the aspects of temperature, pressure and oxidation of nitric acid, and is mainly reflected in that:
after the original reverberatory furnace roasting is changed into rotary kiln roasting with relatively light air pollution in the production of industrial molybdenum oxide, the ammonium insoluble molybdenum and insoluble molybdate in the produced industrial molybdenum oxide have high components and low soluble molybdenum conversion rate due to poor oxidation effect, and the yield of ammonium molybdate is further reduced. Meanwhile, the conventional acid washing operation method has poor impurity removal effect aiming at a certain special ore species, and cannot achieve the condition of solving the problem that part of molybdate which is difficult to dissolve in ammonia water is converted into soluble molybdenum in an acid washing operation mode, so that when ammonia leaching is carried out in a subsequent ammonia leaching working section, the content of residual molybdenum in ammonia leaching residue after ammonia leaching solution is extracted is higher and even can reach 20% due to the fact that low-valence molybdate in molybdenum oxide cannot dissolve in ammonia water, and the recovery rate index of ammonium molybdate production and the economic benefit of enterprises are seriously influenced.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for producing ammonium molybdate, which can greatly improve the pickling effect, thereby improving the yield of ammonium molybdate, reducing the production cost of ammonium molybdate and improving the economic benefit.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention provides a method for producing ammonium molybdate, which comprises the following steps:
s1: carrying out acid washing operation on solid industrial molybdenum oxide, and carrying out solid-liquid separation after the acid washing operation to obtain acid washing liquid and a filter cake;
s2: recovering molybdenum in the pickling solution, and treating the filter cake by an ammonia leaching process to obtain ammonia leaching solution and ammonia leaching residue;
s3: and (3) carrying out acid precipitation treatment on the ammonia leaching solution obtained in the step (S2) to obtain ammonium molybdate and acid precipitation mother liquor, and returning the acid precipitation mother liquor to the acid washing operation for reuse.
Further, in the step S1, the pickling operation is performed in a high-pressure reaction vessel, and the pressure of the pickling operation is maintained at 0.6 to 0.8MPa.
Further, the reaction step of S1 includes:
s11: preparing industrial molybdenum oxide and acid precipitation mother liquor into acid washing slurry according to the solid-liquid ratio of 1:3-7, and adding an oxidation auxiliary agent into the acid washing slurry;
s12: by HNO 3 Adjusting the pH value of the acid washing slurry to 0.5-1, reacting for 1-4 h at 160-170 ℃, and then carrying out solid-liquid separation to obtain acid washing liquid and a filter cake.
Furthermore, the oxidation assistant in s11 is KMnO 4 And H 2 O 2 。
Further, the amount of the oxidation assistant added in s11 is 5 to 10% of the solid phase ratio in the acid-washed slurry.
Further, the acid in the acid precipitation mother liquor in s11 is HNO 3 。
Further, the S2 adopts the following method to recover the molybdenum: and adsorbing and recovering molybdenum by adopting an anion exchange resin column, and desorbing by using ammonia water after adsorption to obtain a solution containing ammonium molybdate.
Further, the solution containing ammonium molybdate is delivered to an ammonia leaching process to be combined with an ammonia leach liquor and used with the ammonia leach liquor to prepare ammonium molybdate.
Further, the ammonia leaching process in S2 is specifically as follows: counter-current leaching the acid-washed filter cake 2-4 times by strong ammonia water, maintaining the leaching temperature at 60-70 ℃, and leaching for 30-80 min each time to obtain ammonia leaching solution.
Further, the acid precipitation treatment method in the S3 comprises the following steps:
s31: adding a proper amount of ammonium sulfide into the ammonia leaching solution, removing the precipitate, and reserving a liquid part;
s32: adding nitric acid into the liquid part for neutralization and crystallization, and controlling the initial specific gravity of the solution to be 1.16-1.18 g/cm 3 The initial temperature is 40-60 ℃, the nitric acid is added first and then slowly, the pH value of the acid addition end point is controlled to be 2.0-2.5, the generated white crystals are separated and dried to obtain an ammonium molybdate product, and the acid precipitation mother liquor generated by separation is returned to the acid washing operation for reuse.
Compared with the prior art, the invention has the beneficial effects that:
according to the ammonium molybdate production method provided by the invention, the normal-pressure acid washing operation process is redesigned on the basis of the conventional ammonium molybdate production process, the original normal-pressure design idea is broken through, the frame of the original process is broken through, a pressure container is creatively used as reaction equipment, the molecular structure form of low-price insoluble molybdate is destroyed under the high-temperature and high-pressure condition, the defect that the oxidation strength of nitric acid is insufficient in the acid washing process is overcome by taking potassium permanganate as an oxidant, and the molybdate insoluble in ammonia water is promoted to obtain sufficient oxidation reaction under the new process condition, so that the molybdate is completely converted into soluble molybdic acid. The method for producing ammonium molybdate has stronger adaptability to the selection of raw materials for producing ammonium molybdate, can adapt to the industrial molybdenum oxide formed by roasting polymetallic ores with high impurity content, solves the limitation that normal-pressure acid washing is carried out when the low-price molybdenum of the industrial molybdenum oxide is too high to completely convert the industrial molybdenum oxide, improves the molybdenum leaching rate of the subsequent ammonia leaching process, reduces the molybdenum content in the ammonia leaching slag, and can greatly improve the economic benefit of molybdenum chemical enterprises.
Drawings
FIG. 1 is a schematic flow chart of a method for producing ammonium molybdate according to an embodiment of the invention;
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents, instruments and the like used are, unless otherwise specified, reagents and materials commercially available. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
Example 1
Referring to fig. 1, this embodiment is a first embodiment of the present invention, and the method for producing ammonium molybdate provided in this embodiment includes the following specific steps:
s1: carrying out acid washing operation on solid industrial molybdenum oxide by adopting a high-pressure reaction vessel, wherein the pressure of the acid washing operation is maintained at 0.6Mpa, and when the acid washing operation is carried out specifically, preparing acid washing slurry from the industrial molybdenum oxide and acid precipitation mother liquor according to the solid-liquid ratio of 1:3, wherein the acid precipitation mother liquor is the acid precipitation mother liquor generated in the step S3; meanwhile, when the pickling operation is carried out, an oxidation assistant KMnO is added into the pickling slurry 4 And H 2 O 2 The oxidation assistant KMnO 4 And H 2 O 2 The addition mass of (A) is 5% of the solid phase proportion in the acid pickling slurry, and KMnO 4 And H 2 O 2 The mass ratio of 1:1, and KMnO is utilized while adding the oxidation auxiliary agent 4 The most oxidizing property under the acidic condition, and the pH value of the slurry is adjusted to 1 by nitric acidKeeping the temperature at 170 ℃ for reaction for 1.5 to 2 hours, wherein the insoluble molybdate in the slurry is KMnO under the action of high temperature and high pressure 4 Decomposing under the action of ultra-strong oxidation, converting the previous ammonia insoluble molybdenum into soluble molybdenum, removing various impurities more thoroughly, and performing solid-liquid separation after the reaction to obtain pickling solution and filter cake;
s2: the filter cake is treated by adopting an ammonia leaching process to obtain ammonia leaching solution and ammonia leaching residue, and the specific operation is as follows: carrying out countercurrent leaching on the acid-washed filter cake for 3 times by adopting concentrated ammonia water, maintaining the leaching temperature at 60 ℃, and combining the leaching solutions for multiple times to obtain ammonia leaching solution, wherein the leaching time is 30min each time;
recovering soluble molybdenum in the pickling solution by adopting anion exchange resin, desorbing by using ammonia water after adsorption to obtain a solution containing ammonium molybdate, and combining the solution containing ammonium molybdate with the ammonia leaching solution;
s3: and (3) carrying out acid precipitation treatment on the ammonia leaching solution obtained in the step (S2) to obtain ammonium molybdate and acid precipitation mother liquor, and returning the acid precipitation mother liquor to the acid washing operation for reuse, wherein the acid precipitation mother liquor specifically comprises the following steps:
firstly, adding a proper amount of ammonium sulfide into the ammonia immersion liquid to purify the ammonia immersion liquid, and then removing precipitates to leave a liquid part;
then, adding nitric acid into the liquid part to perform neutralization crystallization, and controlling the initial specific gravity of the solution to be 1.16-1.18 g/cm 3 And (2) controlling the initial temperature to be 40 ℃, adding nitric acid at a first speed and then at a second speed, controlling the acid addition end point to be pH 2.0-2.5, separating and drying the generated white crystals to obtain an ammonium molybdate product, and returning the acid precipitation mother liquor generated by separation to the acid washing operation, namely recycling in the step S1.
Example 2
Referring to fig. 1, this embodiment is a first embodiment of the present invention, and the method for producing ammonium molybdate provided in this embodiment includes the following specific steps:
s1: the method comprises the steps of carrying out acid washing operation on solid industrial molybdenum oxide by adopting a high-pressure reaction vessel, maintaining the pressure of the acid washing operation at 0.8Mpa, and preparing the industrial molybdenum oxide and acid precipitation mother liquor according to the solid-liquid ratio of 1:5 during the specific acid washing operationSlurry, wherein the acid precipitation mother liquor is the acid precipitation mother liquor generated in the step S3; meanwhile, when the pickling operation is carried out, an oxidation assistant KMnO is added into the pickling slurry 4 And H 2 O 2 The oxidation assistant KMnO 4 And H 2 O 2 The addition mass of (A) is 7% of the solid phase proportion in the acid pickling slurry, and KMnO 4 And H 2 O 2 The mass ratio of 1:1, and KMnO is utilized while adding the oxidation auxiliary agent 4 Adjusting pH value of the slurry to 1 with nitric acid, maintaining temperature at 170 deg.C, and reacting for 1.5 hr, wherein the insoluble molybdate in the slurry is KMnO under high temperature and high pressure 4 Decomposing under the action of ultra-strong oxidation, converting the previous ammonia insoluble molybdenum into soluble molybdenum, removing various impurities more thoroughly, and performing solid-liquid separation after the reaction to obtain pickling solution and filter cake;
s2: the filter cake is treated by adopting an ammonia leaching process to obtain ammonia leaching solution and ammonia leaching residue, and the specific operation is as follows: carrying out countercurrent leaching on the acid-washed filter cake for 2 times by adopting concentrated ammonia water, keeping the leaching temperature at 60-70 ℃, and combining leaching solutions for multiple times to obtain ammonia leaching solution, wherein the leaching time is 65min each time;
and recovering soluble molybdenum in the pickling solution by adopting anion exchange resin, desorbing by using ammonia water after adsorption to obtain a solution containing ammonium molybdate, combining the solution containing ammonium molybdate and the ammonia leaching solution, and conveying the solution containing ammonium molybdate and the ammonia leaching solution to an S3 section together for acid precipitation.
S3: and (3) carrying out acid precipitation treatment on the ammonia leaching solution obtained in the step (S2) to obtain ammonium molybdate and acid precipitation mother liquor, and returning the acid precipitation mother liquor to the acid washing operation for reuse, wherein the acid precipitation mother liquor specifically comprises the following steps:
firstly, adding a proper amount of ammonium sulfide into the ammonia immersion liquid to purify the ammonia immersion liquid, and then removing precipitates to leave a liquid part;
then, adding nitric acid into the liquid part to perform neutralization crystallization, and controlling the initial specific gravity of the solution to be 1.16-1.18 g/cm 3 The initial temperature is 50 ℃, the nitric acid is added at first, then, the nitric acid is added at first, the acid adding end point is controlled to be pH 2.0-2.5, and the generated white crystals are separated and dried, namely, the white crystals are obtainedAnd (4) obtaining an ammonium molybdate product, and returning acid precipitation mother liquor generated by separation to the acid washing operation, namely recycling in the step S1.
Example 3
Referring to fig. 1, this embodiment is a third embodiment of the present invention, and the method for producing ammonium molybdate provided in this embodiment includes the following specific steps:
s1: carrying out acid washing operation on solid industrial molybdenum oxide by adopting a high-pressure reaction vessel, wherein the pressure of the acid washing operation is maintained at 0.7Mpa, and when the acid washing operation is carried out specifically, preparing acid washing slurry from the industrial molybdenum oxide and acid precipitation mother liquor according to the solid-liquid ratio of 1:7, wherein the acid precipitation mother liquor is the acid precipitation mother liquor generated in the step S3; meanwhile, when the pickling operation is carried out, an oxidation assistant KMnO is added into the pickling slurry 4 And H 2 O 2 The oxidation assistant KMnO 4 And H 2 O 2 The addition mass of (A) is 10% of the solid phase proportion in the acid pickling slurry, and KMnO 4 And H 2 O 2 The mass ratio of 1:1, and KMnO is utilized while adding the oxidation auxiliary agent 4 Adjusting the pH value of the slurry to 0.5 by using nitric acid, keeping the temperature at 170 ℃ and reacting for 2h, wherein the difficultly soluble molybdate in the slurry is KMnO under the action of high temperature and high pressure 4 Decomposing under the action of ultra-strong oxidation, converting the previous ammonia insoluble molybdenum into soluble molybdenum, removing various impurities more thoroughly, and performing solid-liquid separation after the reaction to obtain pickling solution and filter cake;
s2: the filter cake is treated by adopting an ammonia leaching process to obtain ammonia leaching solution and ammonia leaching residue, and the specific operation is as follows: carrying out countercurrent leaching on the acid-washed filter cake for 4 times by adopting concentrated ammonia water, maintaining the leaching temperature at 70 ℃, wherein the leaching time is 80min each time, and combining the leaching solutions for multiple times to obtain ammonia leaching solution;
recovering soluble molybdenum in the pickling solution by adopting anion exchange resin, desorbing by using ammonia water after adsorption to obtain a solution containing ammonium molybdate, combining the solution containing ammonium molybdate with the ammonia leaching solution, and conveying to the step S3 for acid precipitation;
s3: and (3) carrying out acid precipitation treatment on the ammonia leaching solution obtained in the step (S2) to obtain ammonium molybdate and acid precipitation mother liquor, and returning the acid precipitation mother liquor to the acid washing operation for reuse, wherein the acid precipitation mother liquor specifically comprises the following steps:
firstly, adding a proper amount of ammonium sulfide into the ammonia immersion liquid to purify the ammonia immersion liquid, and then removing precipitates to leave a liquid part;
then, adding nitric acid into the liquid part to perform neutralization crystallization, and controlling the initial specific gravity of the solution to be 1.16-1.18 g/cm 3 And (2) controlling the initial temperature to be 60 ℃, adding nitric acid at a first speed and a second speed, controlling the acid addition end point to be pH 2.5, separating and drying the generated white crystals to obtain an ammonium molybdate product, and returning the acid precipitation mother liquor generated by separation to the acid washing operation, namely recycling in the step S1.
Example 4
This embodiment is a fourth embodiment of the present invention, and the acid washing operation of the ammonium molybdate production method provided in this embodiment is different from that in embodiments 1 to 3, and the ammonium molybdate production method specifically includes the following steps:
s1: adding a proper amount of nitric acid mixed solution into industrial molybdenum oxide and ammonium nitrate to serve as pickling solution, and carrying out pickling operation in a normal-pressure reaction kettle according to a solid-to-liquid ratio of 1:5, wherein the pickling solution is obtained by adding a proper amount of nitric acid into acid precipitation mother liquor, the pH value is kept at 1 in the pickling process, the pickling time is 1.5h, the temperature is controlled between 85 and 92 ℃, the pickling solution has the effects that impurities in the industrial molybdenum oxide, such as Na, K, cu, pb, fe, mg and the like, are washed away by a nitric acid method, part of low-valence insoluble molybdate in molybdenum trioxide is converted into molybdic acid, and after the reaction is finished, solid-liquid separation is carried out to obtain the pickling solution and a filter cake;
s2: reference example 2;
s3: refer to example 2.
In this example, the composition of the pickling solution was changed from that of example 2.
Example 5
This embodiment is a fifth embodiment of the present invention, and the acid washing operation of the ammonium molybdate production method provided in this embodiment is different from that of embodiment 4, and the ammonium molybdate production method specifically includes the following steps:
s1: taking a mixed solution of industrial molybdenum oxide, ammonium nitrate and a proper amount of nitric acid as a pickling solution, and carrying out pickling operation in a normal-pressure reaction kettle according to a solid-to-liquid ratio of 1:5, wherein the pickling solution is derived from acid precipitation mother liquor, the proper amount of nitric acid is added, the pH value is kept at 1 in the pickling process, the pickling time is 4 hours, the temperature is controlled between 95 and 100 ℃, the pickling solution has the effects that impurities in the industrial molybdenum oxide, such as Na, K, cu, pb, fe, mg and the like, are washed away by a nitric acid method, part of low-valence insoluble molybdate in the molybdenum is converted into molybdic acid, and after the reaction is finished, solid-liquid separation is carried out to obtain the pickling solution and a filter cake;
s2: reference example 4;
s3: refer to example 4.
In this example, the pickling temperature was increased and the pickling time was prolonged based on example 4.
Example 6
This embodiment is a sixth embodiment of the present invention, and the acid washing operation of the ammonium molybdate production method provided in this embodiment is different from that of embodiments 1 to 5, and the specific steps of the ammonium molybdate production method are as follows:
s1: adding water into industrial molybdenum oxide, and preparing pickling slurry by using a high-pressure reaction kettle as a reaction vessel according to a solid-to-liquid ratio of 1:5, wherein during pickling operation, a proper amount of nitric acid is used as an oxidant to adjust the pH value in the pickling process to keep 1, the pickling time is 1.5-2 h, and the temperature is controlled to be 170 ℃, so that impurities in the industrial molybdenum oxide, such as Na, K, cu, pb, fe, mg and the like, are washed away by a nitric acid method, part of low-valence insoluble molybdate in molybdenum trioxide is converted into molybdic acid, and after the reaction is finished, solid-liquid separation is performed to obtain pickling solution and a filter cake;
s2: reference example 2;
s3: refer to example 2.
In this example, the composition of the pickling solution was changed from that of example 2, and high-pressure pickling was employed.
Example 7
This example is a comparative example of the present invention, and the ammonia leaching residue index generated in the process of preparing ammonium molybdate in examples 1 to 6 is tested to determine the effect of the acid washing process on the recovery rate of ammonium molybdate, and the experimental results are shown in table 1 (in which, two experiments are performed in examples 2 and 5, and two sets of experimental data are provided, respectively, example 1, example 3, example 4, and example 5 each provide one set of experimental data):
TABLE 1 indexes of ammonia-leaching residues of examples 1 to 6
Note: the total molybdenum and insoluble molybdenum in table 1 are the total molybdenum content in the raw material;
it can be seen from the above comparative data that, after the acid pickling operation in the ammonium molybdate production method provided by the invention is used for carrying out acid pickling operation on the molybdenum concentrate, the insoluble molybdenum content can be greatly reduced and the ammonia leaching rate can be improved, so that the production and preparation cost of ammonium molybdate can be effectively reduced and the resource can be saved.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (9)
1. The production method of ammonium molybdate is characterized by comprising the following steps:
s1: carrying out acid washing operation on solid industrial molybdenum oxide, and carrying out solid-liquid separation after the acid washing operation to obtain acid washing liquid and a filter cake;
s2: recovering molybdenum in the pickling solution, and treating the filter cake by an ammonia leaching process to obtain ammonia leaching solution and ammonia leaching residue;
s3: and (3) carrying out acid precipitation treatment on the ammonia leaching solution obtained in the step (S2) to obtain ammonium molybdate and acid precipitation mother liquor, and returning the acid precipitation mother liquor to the acid washing operation for reuse.
2. The method for producing ammonium molybdate according to claim 1, wherein the reaction conditions of S1 are as follows: the high-pressure reaction vessel is adopted for acid washing operation, and the pressure of the acid washing operation is maintained at 0.6-0.8 MPa.
3. The method for producing ammonium molybdate according to claim 1, wherein: the reaction step of S1 comprises:
s11: preparing industrial molybdenum oxide and acid precipitation mother liquor into acid washing slurry according to the solid-liquid ratio of 1:3-7, and adding an oxidation auxiliary agent into the acid washing slurry;
s12: by HNO 3 Adjusting the pH value of the acid washing slurry to 0.5-1, reacting for 1-4 h at 160-170 ℃, and then carrying out solid-liquid separation to obtain acid washing liquid and a filter cake.
4. The method for producing ammonium molybdate according to claim 3, wherein: the oxidation auxiliary agent in s11 is KMnO 4 And H 2 O 2 。
5. The method for producing ammonium molybdate according to claim 3, wherein: the addition mass of the oxidation auxiliary agent in s11 is 5-10% of the solid phase proportion in the acid pickling slurry, and KMnO 4 And H 2 O 2 Is 1:1.
6. The method for producing ammonium molybdate according to claim 3, wherein: the acid in the acid precipitation mother liquor in s11 is HNO 3 。
7. The method for producing ammonium molybdate according to claim 1, wherein S2 recovers molybdenum by the following method: and adsorbing and recovering molybdenum by adopting an anion exchange resin column, and desorbing by using ammonia water after adsorption to obtain a solution containing ammonium molybdate.
8. The method for producing ammonium molybdate according to claim 1, wherein the ammonia leaching process in S2 is as follows: and (3) carrying out countercurrent leaching on the acid-washed filter cake for 2-4 times by adopting concentrated ammonia water, wherein the leaching temperature is maintained at 60-70 ℃, and the leaching time is 30-80 min each time, so as to obtain an ammonia leaching solution.
9. The method for producing ammonium molybdate according to claim 1, wherein the acid precipitation treatment method in S3 comprises the following steps:
s31: adding a proper amount of ammonium sulfide into the ammonia leaching solution, removing the precipitate, and reserving a liquid part;
s32: adding nitric acid into the liquid part for neutralization and crystallization, and controlling the initial specific gravity of the solution to be 1.16-1.18 g/cm 3 The initial temperature is 40-60 ℃, the nitric acid is added first and then slowly, the pH value of the acid addition end point is controlled to be 2.0-2.5, the generated white crystals are separated and dried to obtain an ammonium molybdate product, and the acid precipitation mother liquor generated by separation is returned to the acid washing operation for reuse.
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