CN111470537A - Ammonium molybdate recovery method and method for removing impurity tungsten in ammonium molybdate - Google Patents
Ammonium molybdate recovery method and method for removing impurity tungsten in ammonium molybdate Download PDFInfo
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- 235000018660 ammonium molybdate Nutrition 0.000 title claims abstract description 124
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 title claims abstract description 120
- 229940010552 ammonium molybdate Drugs 0.000 title claims abstract description 120
- 239000011609 ammonium molybdate Substances 0.000 title claims abstract description 120
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 107
- 239000010937 tungsten Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000012535 impurity Substances 0.000 title claims abstract description 59
- 238000011084 recovery Methods 0.000 title description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 90
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 78
- 239000002253 acid Substances 0.000 claims abstract description 76
- 239000000047 product Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 93
- 239000011733 molybdenum Substances 0.000 claims description 93
- 229910052750 molybdenum Inorganic materials 0.000 claims description 91
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003723 Smelting Methods 0.000 description 16
- 238000001556 precipitation Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000003916 acid precipitation Methods 0.000 description 8
- 239000003957 anion exchange resin Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 5
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of chemical industry, in particular to a method for recovering ammonium molybdate and a method for removing impurity tungsten in ammonium molybdate. The provided method for recovering ammonium molybdate comprises the following steps: (1) based on a tungsten-containing ammonium molybdate solution, heating to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate; (2) dissolving the first ammonium molybdate precipitate, heating the obtained solution to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a second ammonium molybdate precipitate. The tungsten content in the obtained ammonium molybdate product is little and not more than 100ppm, and the method has the advantages of simple process and low cost and is suitable for industrial production and application.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for recovering ammonium molybdate and a method for removing impurity tungsten in ammonium molybdate.
Background
The elements tungsten and molybdenum belong to VIB group and have very similar chemical properties, and finding the difference in the properties of the elements tungsten and molybdenum and separating the elements tungsten and molybdenum is always a difficult problem for the research of metallurgy and chemists.
With the increasing treatment of high-tungsten molybdenite, nickel-molybdenum ore, waste catalysts and the like, the problem of removing impurity tungsten is also faced in the molybdenum smelting industry. At present, the following two methods are mainly used for removing a small amount of tungsten in ammonium molybdate: one is an ion exchange method which utilizes molybdate radical and tungstic acidThe method has wide adaptability and high automation degree, thereby having wide application range in the industry. However, the method has low direct yield of molybdenum, molybdenum is also adsorbed in a large amount while the resin adsorbs tungsten, the adsorption efficiency is not high, and the subsequent treatment process is long. Another type is a selective adsorption process, using Fe (OH)3The adsorption method is used for removing tungsten in the ammonium molybdate solution, but the method has insufficient separation depth, large molybdenum loss and large amount of generated slag, and a process for recovering the slag is required to be added subsequently.
Therefore, the development of a new process for recovering ammonium molybdate, particularly removing a small amount of tungsten from a solution containing ammonium molybdate and tungsten, is a problem to be solved urgently in the industry.
Disclosure of Invention
The method for recovering ammonium molybdate is convenient and rapid, and can recover ammonium molybdate with low cost, the method for recovering ammonium molybdate has high yield, short process and low cost, the tungsten content of the prepared ammonium molybdate product is less than or equal to 100ppm, and the method meets the international standard of GBT 3460-. The method is suitable for recovering ammonium molybdate in molybdenum smelting industry, especially suitable for removing a small amount of tungsten in the ammonium molybdate, and the depth of removing tungsten is high.
Specifically, the invention provides the following technical scheme:
in a first aspect of the invention, the invention provides a process for recovering ammonium molybdate comprising: (1) based on a tungsten-containing ammonium molybdate solution, heating to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate; (2) dissolving the first ammonium polymolybdate precipitate, heating the obtained solution to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a second ammonium polymolybdate precipitate. The obtained second ammonium molybdate precipitate has little tungsten content which does not exceed 100ppm and meets the standard of national standard GBT 3460-2017.
According to the method for recovering ammonium molybdate, the pH value of the solution is reduced by adding acid, tungsten and molybdenum can form corresponding ammonium tungstate and ammonium molybdate precipitates in the process of reducing the pH value, based on the difference of the precipitation pH conditions of the tungsten and the molybdenum, the ammonium molybdate can complete precipitation at the pH value of 2.5-3, and the tungsten begins to precipitate when the pH value is 2. Therefore, by controlling the pH condition of the solution to be 2.5-3, ammonium molybdate precipitate can be obtained at the moment, and tungsten stays in the solution, so that the good tungsten-molybdenum separation effect is achieved. Meanwhile, in order to deeply remove tungsten, the obtained ammonium molybdate precipitate is dissolved, the steps are repeated at least once again to obtain an ammonium molybdate solution, and the tungsten content in the obtained ammonium molybdate product can be controlled to be below 100 ppm.
According to an embodiment of the present invention, the above method for recovering ammonium molybdate may further comprise the following technical features:
in some embodiments of the present invention, the acid is added in step (1) for 2 to 4 hours, and the addition of the acid to generate the ammonium polymolybdate precipitate is performed for a period of time that affects the amount of impurities in the generated first ammonium polymolybdate precipitate to a certain extent, for example, if the acid is added for a too short period of time, the pH of the solution is rapidly decreased in a short period of time, so that it is not easy to control the pH change, and on the other hand, a part of the tungsten also generates a corresponding precipitate, which degrades the removal effect of tungsten impurities as the first ammonium polymolybdate precipitates.
In some embodiments of the present invention, the acid is added in step (2) for 2.5 to 4 hours, and considering that the first ammonium polymolybdate precipitate may contain a small amount of tungsten impurities, the pH may be adjusted by adding acid to form the ammonium polymolybdate precipitate, and tungsten may remain in the solution, as described above, the addition of acid to form the ammonium polymolybdate precipitate may affect the amount of impurities in the first ammonium polymolybdate precipitate to a certain extent, for example, the acid may be added for too long a period of time, the pH of the solution may be rapidly decreased in a short period of time, on the one hand, it is not easy to control the pH change, on the other hand, a portion of tungsten may also form a corresponding precipitate, and as the first ammonium polymolybdate precipitates, thus deteriorating the removal of tungsten impurities, for example, the acid may be added for too long a period of time, which may also result in a long operation time, and may be applied industrially with increased cost, the acid addition is controlled for 2 to 4 hours, which may effectively remove tungsten impurities, and preferably, the pH of the acid solution may be added in step (2) in a manner of adding hydrogen ion, and the acid solution may be added under a more effective pH-5/5, 355, whereby the condition of the acid solution may be changed.
In some embodiments of the invention, the acid in step (1) and step (2) each independently comprises at least one selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid. Thereby facilitating rapid adjustment of changes in the pH conditions of the solution.
In some embodiments of the present invention, the concentration of the hydrogen-containing ions in the acid solution in the step (1) and the step (2) is 3 to 8 mol/L, preferably 5 to 7 mol/L.
In some embodiments of the present invention, the ammonium molybdate solution containing tungsten in step (1) is calculated by using molybdenum and tungsten trioxide, and the mass ratio of molybdenum to tungsten is 10-50: 1. The mass ratio of molybdenum and tungsten is determined by combining solutions from molybdenum smelting industry, the mass ratio of molybdenum and tungsten in the general production smelting process is in the range, if the mass ratio is not in the range, for example, the mass ratio of molybdenum to tungsten is less than 10:1, which indicates that the content of tungsten is high, the method also has a certain tungsten-molybdenum separation effect, but the content of tungsten in the obtained ammonium molybdate product exceeds the standard, and tungsten needs to be further removed. The method is also applicable when the mass ratio of molybdenum to tungsten is more than 50:1, but when the mass ratio of molybdenum to tungsten is higher, acid precipitation is not needed for two times, and qualified ammonium molybdate products can be obtained by one time of acid precipitation.
In some embodiments of the present invention, in step (1), the concentration of molybdenum in the ammonium molybdate solution containing tungsten is 40-140 g/L calculated by using molybdenum as a simple substance, the molybdenum concentration is controlled mainly based on the requirement of the molybdenum concentration in the solution by the acid precipitation process, when the molybdenum concentration in the solution is too high, the rate of aggregation of precipitation ions is high, the number of formed crystal nuclei is large, the precipitation ions are extremely fine and difficult to grow, only fine precipitates can be obtained, the impurity content is also high, and on the contrary, when the solution concentration is too low, although good precipitates can be obtained, the precipitation yield is reduced, and the loss of mother liquor and molybdenum is increased, therefore, in order to ensure the yield and quality, the molybdenum concentration before acid precipitation can be controlled to be 40-140 g/L.
In some embodiments of the present invention, the concentration of molybdenum in the solution obtained after dissolving and precipitating the first ammonium polymolybdate is 110-140 g/L, calculated by molybdenum as simple substance in step (2).
In some embodiments of the invention, step (1) further comprises: (1-1) heating to 40-60 ℃ based on an ammonium molybdate solution containing tungsten, and adding acid until the pH value of the solution is 2.5-3; (1-2) when the pH value of the solution is 2.5-3 and no acid is added, continuing the reaction for no more than 2 hours, and separating to obtain a first ammonium molybdate precipitate. Whereby a further precipitation of ammonium polymolybdate can be obtained.
In some embodiments of the present invention, in the step (2), the first ammonium polymolybdate precipitate is dissolved by ammonia water, the first ammonium polymolybdate precipitate may be dissolved by ammonia water to obtain an ammonium molybdate solution, and a suitable concentration of the ammonia water may be 0.5 to 1.5 mol/L.
In some embodiments of the invention, the method further comprises: and (3) dissolving the second ammonium polymolybdate precipitate, and crystallizing the obtained solution to obtain an ammonium molybdate product. Wherein, when the crystallization is carried out, an evaporation crystallization mode or an evaporation concentration cooling crystallization mode can be utilized.
In some embodiments of the invention, the tungsten content in the second ammonium molybdate precipitate or the ammonium molybdate product does not exceed 100ppm, optionally with a direct yield of molybdenum above 90%.
In a second aspect of the invention, the method for purifying ammonium molybdate comprises the steps of (1) heating an ammonium molybdate solution containing tungsten with molybdenum concentration of 40-140 g/L to 40-60 ℃, adding acid to the pH value of the solution of 2.5-3 so as to separate and obtain a first ammonium molybdate precipitate, controlling the adding time of the acid to be 2-4 hours, (2) dissolving the first ammonium molybdate precipitate, heating the obtained solution with molybdenum concentration of 110-140 g/L to 40-45 ℃, adding an acid solution to the pH value of 2.5-3 so as to separate and obtain a second ammonium molybdate precipitate, controlling the adding time of the acid to be 2.5-3 hours, and (3) dissolving the second ammonium molybdate precipitate, and crystallizing the obtained precipitate so as to obtain an ammonium molybdate product.
In a third aspect of the invention, the method for removing impurity tungsten in ammonium molybdate comprises the steps of (1) heating to 40-60 ℃ based on a tungsten-containing ammonium molybdate solution with molybdenum concentration of 40-140 g/L, adding acid to a solution pH value of 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate and a first impurity solution, controlling the adding time of the acid to be 2-4 hours, (2) dissolving the first ammonium polymolybdate precipitate, heating the obtained solution with molybdenum concentration of 110-140 g/L to 40-45 ℃, adding acid to a solution pH value of 2.5-3 so as to separate and obtain a second ammonium polymolybdate precipitate and a second impurity solution, controlling the adding time of the acid to be 2.5-3 hours, (3) dissolving the second ammonium polymolybdate precipitate, crystallizing the obtained precipitate so as to obtain an ammonium molybdate product, and (4) combining the first impurity solution and the second impurity solution, recovering tungsten from a weakly alkaline cation exchange resin, wherein the ammonium polymolybdate product can be recovered by using a weakly alkaline cation exchange resin, and the ammonium molybdate product can be recovered by using 100ppm of tungsten.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention. Also, certain terms used herein are explained and illustrated to facilitate understanding by those skilled in the art, and it is to be understood that such explanation and illustration are only for convenience of understanding and should not be construed as limiting the scope of the present invention.
As used herein, reference to "ammonium molybdate" is to be understood in a broad sense to include not only the individual ammonium molybdate as is commonly referred to (formula H8MON2O4), but also ammonium polymolybdates such as ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, and the like. The ammonium polymolybdate referred to comprises at least two of the individual ammonium molybdates shown above. The ammonium molybdate recovered by the provided method can exist in the form of single ammonium molybdate or multiple ammonium molybdates, wherein the multiple ammonium molybdate can exist in multiple forms such as ammonium dimolybdate, ammonium tetramolybdate and the like, and can also exist in a mixed form.
In the research process, the inventor of the invention finds that tungsten and molybdenum can be precipitated under different pH conditions, for example, ammonium molybdate is precipitated at the pH value of 2.5-3, and tungsten begins to precipitate when the pH value is below 2, so that the pH value in the solution is controlled to be 2.5-3, so that ammonium molybdate is precipitated, tungsten is not precipitated and remains in the solution, and the good effect of separating tungsten and molybdenum is obtained. In addition, in order to obtain high-purity molybdenum, tungsten is further removed, the obtained ammonium molybdate precipitate is subjected to solution again, then the pH value in the solution is controlled to be 2.5-3, and the ammonium molybdate product is obtained through precipitation and separation. The tungsten content of the ammonium molybdate product thus obtained does not exceed 100 pm.
To this end, in one aspect of the present invention, there is provided a method for recovering ammonium molybdate comprising: (1) based on a tungsten-containing ammonium molybdate solution, heating to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate; (2) dissolving the first ammonium polymolybdate precipitate, heating the obtained solution to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a second ammonium polymolybdate precipitate.
Generally, the mass ratio of molybdenum to tungsten in the solution obtained by molybdenum smelting is 10-50: 1, the mass ratio of molybdenum to tungsten in the solution obtained by molybdenum smelting is determined by combining the solution from the molybdenum smelting industry, the mass ratio of molybdenum to tungsten in the solution obtained by molybdenum smelting is in the range, if the mass ratio is not in the range, for example, the mass ratio of molybdenum to tungsten is less than 10:1, which indicates that the content of tungsten is high, the method also has a certain tungsten-molybdenum separation effect, but the tungsten content of the obtained ammonium molybdate product is beyond the standard, and further tungsten removal is needed, when the mass ratio of molybdenum to tungsten is more than 50:1, the method is also applicable, but when the mass ratio of molybdenum to tungsten is higher, acid precipitation is not needed twice, and qualified ammonium molybdate products can be obtained by one acid precipitation, the ammonium molybdate solution containing tungsten obtained by molybdenum smelting can be concentrated by heating or diluted by adding water to a proper concentration so as to generate the first ammonium molybdate precipitate, and the concentration of molybdenum in the embodiment of the invention is L g/g of the ammonium molybdate solution.
The acid may be present as an acid solution, and the acid solution may be added while stirring the solution until the pH of the solution is 2.5 to 3. in at least some embodiments of the present invention, the addition time of the acid solution may be controlled to 2 to 4 hours. the concentration of hydrogen ions in the acid solution is controlled to 3 to 6 mol/L. useful acid solutions include, but are not limited to, sulfuric acid, hydrochloric acid, nitric acid, and the like.
And stopping adding the acid when the pH value of the solution is adjusted to 2.5-3. The reaction may then be continued for a period of time not exceeding 2 hours, for example 1 to 2 hours, to further precipitate ammonium polymolybdate. Then, the first ammonium molybdate precipitate and the first tungsten-containing solution are obtained by separation. The separation can be carried out by conventional means, for example by filtration, but also by other means customary in the art. The solution from which the precipitate is removed is a first impurity solution containing a small amount of tungsten and molybdenum, which can be recovered by adsorption on a macroporous weak base anion exchange resin.
In order to further improve the recovery effect of ammonium molybdate, the obtained first ammonium polymolybdate precipitate can be dissolved again to prepare a solution, then an acid is added to adjust the pH value to 2.5-3, ammonium polymolybdate is precipitated, and the ammonium polymolybdate is separated so as to obtain the ammonium polymolybdate.
Firstly, heating a dissolved ammonium molybdate solution to 40-45 ℃, then adding an acid solution while stirring until the pH value of the solution is 2.5-3, and controlling the adding time of the acid solution to be 2.5-3 hours, wherein the usable acid solution comprises, but is not limited to, sulfuric acid, hydrochloric acid, nitric acid and the like, and the concentration of hydrogen ions contained in the acid solution is 5.5-7.5 mol/L.
The second ammonium polymolybdate precipitate is then isolated, and useful isolation means may be those commonly used in the art, such as filtration and the like. The solution after the sediment is removed is a second impurity solution, and the obtained second impurity solution contains a very small amount of tungsten and molybdenum and can be absorbed and recovered by macroporous weak base anion exchange resin. The tungsten content in the second ammonium polymolybdate precipitate is below 100 ppm.
The second ammonium polymolybdate precipitate obtained was predominantly ammonium tetramolybdate. If it is desired to obtain an ammonium molybdate product containing a smaller number of individual ammonium molybdates, the second ammonium polymolybdate obtained can be further dissolved with aqueous ammonia and then subjected to evaporative crystallization. By this method, for example, ammonium dimolybdate can be obtained, the tungsten content of the obtained ammonium dimolybdate product does not exceed 100 ppm. Of course, if it is desired to obtain an ammonium molybdate product containing a larger number of ammonium molybdates, the second ammonium polymolybdate obtained can be further dissolved by using ammonia water, and then subjected to evaporative concentration, cooling and crystallization. By this method, for example, ammonium heptamolybdate can be obtained, and the tungsten content of the obtained ammonium heptamolybdate product does not exceed 100 ppm.
The method can be used for purifying ammonium molybdate, and the invention also provides a method for purifying ammonium molybdate, which comprises (1) heating tungsten-containing ammonium molybdate solution with molybdenum concentration of 40-140 g/L to 40-60 ℃, adding acid to the solution pH value of 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate, and controlling the adding time of the acid to be 2-4 hours;
(2) dissolving the first ammonium polymolybdate precipitate, heating the obtained solution with the molybdenum concentration of 110-140 g/L to 40-45 ℃, adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a second ammonium polymolybdate precipitate, and controlling the adding time of the acid to be 2.5-3 hours;
(3) dissolving the second ammonium polymolybdate precipitate and crystallizing the obtained precipitate to obtain ammonium molybdate product.
In addition, the invention also provides a method for removing impurity tungsten in ammonium molybdate, which comprises the following steps of (1) heating an ammonium molybdate solution containing tungsten and having a molybdenum concentration of 40-140 g/L to 40-60 ℃, adding acid to the solution until the pH value is 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate and a first impurity solution, and controlling the adding time of the acid to be 2-4 hours;
(2) dissolving the first ammonium polymolybdate precipitate, heating the obtained solution with the molybdenum concentration of 110-140 g/L to 40-45 ℃, adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a second ammonium polymolybdate precipitate and a second impurity solution, and controlling the adding time of the acid to be 2.5-3 hours;
(3) decomposing the second ammonium polymolybdate precipitate, and crystallizing the obtained precipitate to obtain an ammonium molybdate product;
(4) combining the first impurity solution and the second impurity solution, and recovering tungsten by using a weakly basic cation exchange resin.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Embodiment 1 provides a method for recovering ammonium molybdate, which specifically includes the following steps:
(1) 350ml of ammonium molybdate solution containing tungsten obtained in the molybdenum smelting process, wherein the concentration of molybdenum in the solution (calculated by simple substance molybdenum, namely the concentration of simple substance molybdenum) is adjusted to 40 g/L3The concentration is 0.8 g/L, and the mass ratio is 50: 1.
(2) The solution was heated to 60 ℃ and 3 mol/L mol hydrochloric acid was added slowly while stirring until the pH of the solution was 2.5 and the hydrochloric acid addition time was controlled to 2 hours.
(3) And after the pH value of the solution reaches 2.5, stopping adding hydrochloric acid, continuing to react for 2 hours, and separating to obtain a first ammonium polymolybdate precipitate and a first impurity solution. Wherein the volume of the first impurity solution obtained is 430ml, WO3The concentration is 0.65g/l, the concentration of Mo (referring to simple substance molybdenum) is 1.26 g/L, the first impurity solution can be directly absorbed and recovered by macroporous weak base anion exchange resin.
(4) Dissolving the ammonium polymolybdate precipitate obtained in the step (3) with 0.5 mol/L ammonia water to obtain 122ml of ammonium molybdate solution, wherein the Mo concentration in the solution is 110 g/L3The concentration was 0.11 g/l.
(5) And (3) heating the ammonium molybdate solution obtained in the step (4) to 40 ℃, and slowly adding concentrated hydrochloric acid to adjust the pH to 2.5 in the stirring process. The addition time of hydrochloric acid was controlled to 2.5 h. And (4) under the condition of the ammonium molybdate solution obtained in the step (4), precipitating by using concentrated hydrochloric acid to obtain white massive ammonium molybdate with uniform and loose particle size.
(6) Immediately filtering the solution after the pH value of the solution reaches 2.5 to obtain ammonium tetramolybdate precipitate and obtain a second impurity solution, wherein the volume of the obtained second impurity solution is 155ml, and the Mo concentration is 0.85 g/L3The concentration is 0.08g/l, and the impurity solution can be absorbed and recovered by macroporous weak base anion exchange resin.
The direct yield of molybdenum is calculated to be 95.2%, and the tungsten content of the obtained ammonium tetramolybdate product is 47ppm, which meets the standard of national standard GBT 3460-. Wherein the direct yield (%) of molybdenum is calculated by the following method:
and subtracting the molybdenum content in the impurity solutions (the first impurity solution and the second impurity solution) generated twice from the molybdenum content in the initial feed liquid to obtain the molybdenum content of the product, and dividing by the molybdenum content in the initial feed liquid to obtain the direct yield of the molybdenum.
Example 2
Embodiment 2 provides a method for recovering ammonium molybdate, which specifically includes the following steps:
(1) 350ml of ammonium molybdate solution containing tungsten obtained in the molybdenum smelting process, wherein the Mo concentration of the solution is 92.6 g/L3The concentration is 3.4g/L, and the mass ratio is 27.2: 1.
(2) The solution is heated to 50 ℃, 4.5 mol/L nitric acid is slowly added during stirring until the pH value of the solution is 2.8, and the adding time of the nitric acid is controlled to be 4 h.
(3) And stopping adding the nitric acid when the pH value of the solution reaches 2.8, and continuing to react for 1h to obtain a first ammonium polymolybdate precipitate and a first impurity solution. Wherein the volume of the first impurity solution obtained is 470ml, WO3The concentration is 2.5g/l, Mo concentration is 3.6 g/L, the first impurity solution can be directly absorbed and recovered by macroporous weak base anion exchange resin.
(4) Dissolving the ammonium polymolybdate precipitate obtained in the step (3) with 1 mol/L ammonia water to obtain 220ml of ammonium molybdate solution, wherein the Mo concentration of the solution is 140 g/L3The concentration was 0.18 g/l.
(5) And (3) heating the ammonium molybdate solution obtained in the step (4) to 45 ℃, slowly adding nitric acid of 5.5 mol/L in the stirring process to adjust the pH to 2.7, and controlling the adding time of the nitric acid to be 2.6 h.
(6) When the pH value of the solution reaches 2.7, immediately filtering to obtain ammonium tetramolybdate precipitate and obtain a second impurity solution, wherein the volume of the obtained second impurity solution is 260ml, and the Mo concentration is 1.15 g/L3The second impurity solution, at a concentration of 0.14g/l, can be recovered by adsorption on a macroporous weak base anion exchange resin.
The direct yield of molybdenum is calculated to be 93.9%, and the tungsten content of the obtained ammonium tetramolybdate product is 63ppm, which meets the standard of national standard GBT 3460-.
Example 3
Embodiment 3 provides a method for recovering ammonium molybdate, which specifically includes the following steps:
(1) 350ml of ammonium molybdate solution containing tungsten obtained in the molybdenum smelting process, wherein the Mo concentration of the solution is 140 g/L3The concentration is 14g/L, and the mass ratio is 10: 1.
(2) The solution is heated to 40 ℃, 3 mol/L of sulfuric acid is slowly added during stirring to adjust the pH value to 2.8, and the adding time of the sulfuric acid is controlled to be 3 hours.
(3) After the pH value of the solution reaches 2.8, ammonium polymolybdate precipitate and a first impurity solution are obtained by immediate filtration. WhereinThe volume of the first impurity solution obtained was 485ml, WO3The concentration is-9.8 g/l, Mo concentration is 9.3 g/L, the first impurity solution can be directly absorbed and recovered by macroporous weak base anion exchange resin.
(4) Dissolving the ammonium polymolybdate precipitate obtained in the step (3) with 1.5 mol/L ammonia water to obtain 356ml of ammonium molybdate solution, wherein the Mo concentration of the solution is 125 g/L3The concentration was 0.23 g/l.
(5) Heating the ammonium molybdate solution obtained in the step (4) to 42 ℃, slowly adding 3.75 mol/L sulfuric acid during stirring to adjust the pH to 3, and controlling the adding time of the sulfuric acid to be 3 h.
(6) Immediately filtering to obtain ammonium tetramolybdate precipitate when pH value of the solution reaches 3, and simultaneously obtaining second impurity solution, wherein volume of the obtained second impurity solution is 426ml, and Mo concentration is 0.92 g/L3The concentration is 0.18g/l, and the impurity solution can be absorbed and recovered by macroporous weak base anion exchange resin.
The calculated direct yield of molybdenum is 90%, and the tungsten content of the obtained ammonium tetramolybdate product is 92ppm and meets the national standard GBT 3460-2017.
Comparative example 1
Comparative example 1 differs from example 2 in that:
comparative example 1 provides a method for recovering ammonium molybdate, comprising the following steps:
(1) 350ml of ammonium molybdate solution containing tungsten obtained in the molybdenum smelting process, wherein the Mo concentration of the solution is 92.6 g/L3The concentration is 3.4g/L, and the mass ratio is 27.2: 1.
(2) The solution is heated to 50 ℃, 4.5 mol/L nitric acid is slowly added during stirring, and the pH value of the solution is 2.0, and the adding time of the nitric acid is controlled to be 4 h.
(3) And after the pH value of the solution reaches 2, stopping adding nitric acid, and continuing to react for 1h to obtain a first ammonium polymolybdate precipitate and a first impurity solution. Wherein the volume of the first impurity solution obtained is 476ml, WO3The concentration was 0.11g/l and the Mo concentration was 0.12 g/L.
Acid precipitation mother liquor WO3Concentration of 0.11g/l, comparison with WO in the original feed liquid3The concentration was 3.4g/l, as can be seen inUnder the condition of pH2, the tungsten precipitation rate is (1-0.11 476/3.4/350) × 100% >, 95.6%.
The experimental results show that:
the result shows that under the condition, the precipitation rate of tungsten is high, and the tungsten and the molybdenum are crystallized into the product as the molybdenum, so that the effect of separating the tungsten and the molybdenum cannot be achieved. Therefore, it is desirable to control the pH to 2.5 or more optimally.
Comparative example 2
Comparative example 2 differs from example 2 in that:
comparative example 2 provides a method for recovering ammonium molybdate, comprising the following steps:
(1) 350ml of ammonium molybdate solution containing tungsten obtained in the molybdenum smelting process, wherein the Mo concentration of the solution is 92.6 g/L3The concentration is 3.4g/L, and the mass ratio is 27.2: 1.
(2) The solution is heated to 50 ℃, 4.5 mol/L nitric acid is slowly added during stirring until the pH value of the solution is 3.5, and the adding time of the nitric acid is controlled to be 4 h.
(3) And stopping adding the nitric acid when the pH value of the solution reaches 3.5, and continuing to react for 1h to obtain a first ammonium polymolybdate precipitate and a first impurity solution. Wherein the volume of the first impurity solution obtained is 466ml, WO3The concentration was 2.5g/l and the Mo concentration was 22.6 g/L.
The concentration of tungsten in the acid precipitation mother liquor is 2.5g/l, compared with WO in the original feed liquid3The concentration was 3.4g/l, and it was found that the tungsten precipitation rate was (1-2.5 x 466/3.4/350) x 100%, (2.1%) at a pH of 3.5.
However, under these conditions, the precipitation rate of molybdenum was (1-22.6 466/350/92.6) 100% — 67.5%, and the direct yield was too low.
The experimental results show that:
when the pH value of the end point is higher, namely the acid addition is not enough, the precipitation rate of the molybdenum is low, the direct yield is too low, and the production cost is increased.
Comparative example 3
Comparative example 3 differs from example 2 in that:
comparative example 3 provides a method for recovering ammonium molybdate, comprising the following steps:
(1) obtained in the molybdenum smelting process350ml of ammonium tungsten-containing molybdate solution, wherein the Mo concentration of the solution is 92.6 g/L3The concentration is 3.4g/L, and the mass ratio is 27.2: 1.
(2) The solution is heated to 50 ℃, 4.5 mol/L nitric acid is rapidly added during stirring until the pH value of the solution is 2.8, and the adding time of the nitric acid is controlled to be 1 h.
(3) And stopping adding the nitric acid when the pH value of the solution reaches 2.8, and continuing to react for 1h to obtain a first ammonium polymolybdate precipitate and a first impurity solution. Wherein the volume of the first impurity solution obtained is 468ml, WO3The concentration was 2.5g/l and the Mo concentration was 8.6 g/L.
Under these conditions, the deposition rate of tungsten was (1-2.5 × 468/350/3.4) × 100% — 1.68%, and the variation was small.
The precipitation rate of molybdenum was (1-8.6 × 468/350/92.6) × 100% — 87.6%. The direct yield is lower than that of example 2.
The experimental results show that:
when the acid addition rate is too high, the molybdenum concentration of the mother liquor is high, resulting in a decrease in the direct yield.
Comparative example 4
Comparative example 4 differs from example 2 in that:
comparative example 4 provides a method for recovering ammonium molybdate, comprising the following steps:
(1) 350ml of ammonium molybdate solution containing tungsten obtained in the molybdenum smelting process, wherein the Mo concentration of the solution is 92.6 g/L3The concentration is 3.4g/L, and the mass ratio is 27.2: 1.
(2) The solution is heated to 50 ℃, 4.5 mol/L nitric acid is rapidly added during stirring until the pH value of the solution is 2.8, and the adding time of the nitric acid is controlled to be 5 h.
(3) And stopping adding the nitric acid when the pH value of the solution reaches 2.8, and continuing to react for 1h to obtain a first ammonium polymolybdate precipitate and a first impurity solution. Wherein the volume of the first impurity solution obtained is 462ml, WO3The concentration was 2.2g/l and the Mo concentration was 2.8 g/L.
Under these conditions, the deposition rate of tungsten was (1-2.2 × 462/350/3.4) × 100% — 14.6%, and the deposition rate was increased.
The precipitation rate of molybdenum was (1-2.8 × 462/92.6/350) × 100% — 96%. The direct yield is increased.
Because the acid adding time is too long, the phase change is equivalent to the prolonging of the reaction time, the precipitation rates of tungsten and molybdenum are improved to different degrees, but the obtained ammonium molybdate precipitate is obviously much finer than that in the example 2, so that the filtration time is prolonged, and the production application is not facilitated.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for recovering ammonium molybdate, comprising:
(1) based on a tungsten-containing ammonium molybdate solution, heating to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate;
(2) dissolving the first ammonium polymolybdate precipitate, heating the obtained solution to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a second ammonium polymolybdate precipitate.
2. The method according to claim 1, wherein the adding time of the acid in the step (1) is controlled to be 2-4 hours, preferably, the acid in the step (1) is added in the form of an acid solution, and the concentration of hydrogen-containing ions in the acid solution is 3-6 mol/L.
3. The method according to claim 1, wherein the acid is added in step (2) for 2.5-4 hours, preferably, the acid is added in step (2) in the form of an acid solution, and the concentration of hydrogen-containing ions in the acid solution is 5.5-7.5 mol/L.
4. The method according to claim 1, wherein the acid in step (1) and step (2) each independently comprises at least one selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid;
preferably, the concentration of the hydrogen-containing ions in the acid solution in the step (1) and the step (2) is 3-8 mol/L, preferably 5-7 mol/L.
5. The method according to claim 1, wherein the ammonium molybdate solution containing tungsten in the step (1) is calculated by molybdenum and tungsten trioxide, and the mass ratio of molybdenum to tungsten is 10-50: 1;
optionally, in the step (1), the concentration of molybdenum in the ammonium molybdate solution containing tungsten is 40-140 g/L calculated by molybdenum simple substance;
optionally, in the step (2), the concentration of molybdenum in the solution obtained after dissolving and precipitating the first ammonium polymolybdate is 110-140 g/L calculated by molybdenum simple substance.
6. The method of claim 1, wherein step (1) further comprises:
(1-1) heating to 40-60 ℃ based on an ammonium molybdate solution containing tungsten, and adding acid until the pH value of the solution is 2.5-3;
(1-2) when the pH value of the solution is 2.5-3 and no acid is added, continuing to react for no more than 2 hours, and separating to obtain a first ammonium molybdate precipitate;
optionally, dissolving the first ammonium polymolybdate precipitate with ammonia water in step (2);
preferably, the concentration of the ammonia water is 0.5-1.5 mol/L.
7. The method of claim 1, further comprising:
dissolving the second ammonium polymolybdate precipitate, and crystallizing the obtained solution to obtain an ammonium molybdate product;
optionally, the crystallization is evaporative crystallization or evaporative concentration cooling crystallization.
8. The process of claim 1 or 7, wherein the tungsten content of the second polymolybdate precipitate or of the ammonium molybdate product does not exceed 100 ppm;
optionally, the direct yield of molybdenum is above 90%.
9. A method of purifying ammonium molybdate, comprising:
(1) based on a tungsten-containing ammonium molybdate solution with molybdenum concentration of 40-140 g/L, heating to 40-60 ℃, and adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate, wherein the adding time of the acid is controlled to be 2-4 hours;
(2) dissolving the first ammonium polymolybdate precipitate, heating the obtained solution with the molybdenum concentration of 110-140 g/L to 40-45 ℃, adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a second ammonium polymolybdate precipitate, and controlling the adding time of the acid to be 2.5-3 hours;
(3) dissolving the second ammonium polymolybdate precipitate and crystallizing the obtained precipitate to obtain ammonium molybdate product.
10. A method for removing impurity tungsten in ammonium molybdate is characterized by comprising the following steps:
(1) based on a tungsten-containing ammonium molybdate solution with molybdenum concentration of 40-140 g/L, heating to 40-60 ℃, adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a first ammonium polymolybdate precipitate and a first impurity solution, and controlling the adding time of the acid to be 2-4 hours;
(2) dissolving the first ammonium polymolybdate precipitate, heating the obtained solution with the molybdenum concentration of 110-140 g/L to 40-45 ℃, adding acid until the pH value of the solution is 2.5-3 so as to separate and obtain a second ammonium polymolybdate precipitate and a second impurity solution, and controlling the adding time of the acid to be 2.5-3 hours;
(3) decomposing the second ammonium polymolybdate precipitate, and crystallizing the obtained precipitate to obtain an ammonium molybdate product;
(4) combining the first impurity solution and the second impurity solution, and recovering tungsten by using a weakly basic cation exchange resin.
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