CN110803715A - Continuous preparation method of ammonium heptamolybdate - Google Patents
Continuous preparation method of ammonium heptamolybdate Download PDFInfo
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Abstract
The invention discloses a continuous preparation method of ammonium heptamolybdate, which comprises the following steps: adding ammonia water into an ammonium dimolybdate aqueous solution to obtain an ammonium molybdate solution; evaporating and concentrating the ammonium molybdate solution to obtain an ammonium heptamolybdate solution; filtering the ammonium heptamolybdate solution to remove impurities; and (3) injecting the filtered and impurity-removed ammonium heptamolybdate solution into a cooling crystallizer for cooling crystallization, starting continuous feeding and intermittent discharging after crystals are separated out, filtering the discharged liquid to obtain a crystallized filter cake, and then sequentially carrying out centrifugal drying and drying on the crystallized filter cake to obtain an ammonium heptamolybdate product. According to the continuous preparation method of ammonium heptamolybdate, the ammonium heptamolybdate product obtained by means of continuous feeding and intermittent discharging is stable in quality and good in fluidity; the content of nitrate impurities in an ammonium heptamolybdate product obtained by adopting ammonium dimolybdate as a raw material is less than 20ppm, the solubility in pure water at 25 ℃ is more than 60g/100ml, and the product has high purity and good solubility.
Description
Technical Field
The invention belongs to the technical field of molybdenum chemical production processes, and particularly relates to a continuous preparation method of ammonium heptamolybdate.
Background
Ammonium heptamolybdate is one of the earliest ammonium molybdate products, has large particle size and good water solubility, is mainly used in industries such as chemical and petroleum catalysts, dyes, pigments and trace fertilizers, and also has application in molybdenum metal processing industry.
The intermittent production process is complex, the equipment is backward, the productivity is low, the purity is poor, the granularity is uneven, the large-scale production is difficult to realize, the wide application of the intermittent production process is restricted, particularly, the catalyst industry requires high purity and good solubility of ammonium heptamolybdate, and the existing products in the domestic market cannot meet the requirements of the catalyst industry.
Disclosure of Invention
The invention aims to provide a continuous preparation method of ammonium heptamolybdate, which solves the problems of low purity, poor solubility and unstable quality of the ammonium heptamolybdate product obtained by the existing intermittent production process.
The technical scheme adopted by the invention is as follows: a continuous preparation method of ammonium heptamolybdate comprises the following steps:
step 1, dissolving: adding ammonia water into an ammonium dimolybdate aqueous solution to obtain an ammonium molybdate solution;
step 2, concentration: evaporating and concentrating the ammonium molybdate solution obtained in the step 1 to obtain an ammonium heptamolybdate solution;
and step 3, filtering: filtering and removing impurities from the ammonium heptamolybdate solution obtained in the step 2;
and 4, cooling and crystallizing: and (3) injecting the ammonium heptamolybdate solution filtered and purified in the step (3) into a cooling crystallizer for cooling crystallization, starting continuous feeding and discharging at intervals after crystals are separated out, filtering the discharged liquid to obtain a crystallized filter cake, and then sequentially carrying out centrifugal drying and drying on the crystallized filter cake to obtain an ammonium heptamolybdate product.
The present invention is also characterized in that,
the mass ratio of ammonium dimolybdate to deionized water in the ammonium dimolybdate aqueous solution obtained in the step 1 is 1: 1.
the mass percentage of molybdenum in the ammonium dimolybdate is not less than 56%.
The concentration of ammonia in step 1 was 25%.
In the step 1, the temperature of the reaction between the ammonium dimolybdate aqueous solution and the ammonia water is 70 ℃, and the pH value is 6.8-7.2.
Controlling the density of the ammonium molybdate solution to be 1.36-1.4g/cm in the evaporation concentration process of the step 23The pH value is 6.3-6.8.
And 4, the volume of the ammonium heptamolybdate solution injected into the cooling crystallizer in the step 4 is 75-80% of the full liquid level of the cooling crystallizer.
In the cooling crystallization process of the step 4, the stirring speed is controlled to be 120-130r/min, and the crystallization temperature is not more than 22 ℃.
The interval time of the material discharging in the step 4 is 15 min.
The cooling crystallizer in the step 4 is a QJ type cooling crystallizer and is made of 316 stainless steel.
The invention has the beneficial effects that: according to the continuous preparation method of ammonium heptamolybdate, the ammonium heptamolybdate product obtained by means of continuous feeding and intermittent discharging is stable in quality and good in fluidity; the content of nitrate impurities in an ammonium heptamolybdate product obtained by adopting ammonium dimolybdate as a raw material is less than 20ppm, the solubility in pure water at 25 ℃ is more than 60g/100ml, and the product has high purity and good solubility.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention provides a continuous preparation method of ammonium heptamolybdate, which comprises the following steps:
step 1, dissolving: taking ammonium dimolybdate in mass ratio: 1:1 deionized water of ammonium dimolybdate, wherein the mass percent of molybdenum in the ammonium dimolybdate is not less than 56%; adding ammonia water with the concentration of 25% into an ammonium dimolybdate aqueous solution, wherein the reaction temperature is 70 ℃, and the pH value is 6.8-7.2, so as to obtain an ammonium molybdate solution;
step 2, concentration: evaporating and concentrating the ammonium molybdate solution obtained in the step 1, and controlling the density of the ammonium molybdate solution to be 1.36-1.4g/cm3Obtaining ammonium heptamolybdate solution with the pH value of 6.3-6.8;
and step 3, filtering: filtering and removing impurities from the ammonium heptamolybdate solution obtained in the step 2;
and 4, cooling and crystallizing: and (3) injecting the filtered and impurity-removed ammonium heptamolybdate solution in the step (3) into a cooling crystallizer for cooling crystallization, wherein the injection volume amount is 75-80% of the full liquid level of the cooling crystallizer, the stirring speed is controlled to be 120-130r/min in the cooling crystallization process, the crystallization temperature is not more than 22 ℃, feeding is started continuously and discharging is started at intervals after crystals are separated out, the interval time of discharging at intervals is 15min, the discharged liquid is filtered to obtain a crystallized filter cake, and then the crystallized filter cake is subjected to centrifugal spin-drying and drying in sequence to obtain an ammonium heptamolybdate product.
According to the continuous preparation method of ammonium heptamolybdate, the ammonium heptamolybdate product obtained by the continuous feeding and interval discharging manner is stable in quality and good in fluidity; the content of nitrate impurities in an ammonium heptamolybdate product obtained by adopting ammonium dimolybdate as a raw material is less than 20ppm, the solubility in pure water at 25 ℃ is more than 60g/100ml, and the product has high purity and good solubility. Meanwhile, the QJ-type cooling crystallizer adopted by the invention is made of 316 stainless steel, can conveniently control the temperature, the pressure and the concentration, provides constant driving force for the crystallization process, is beneficial to the stable control of quality indexes such as product granularity, water solubility and the like, and is also convenient to realize automatic operation.
Example 1
Taking ammonium dimolybdate in mass ratio: 1:1 deionized water, wherein the mass percent of molybdenum in the ammonium dimolybdate is 56.23%; adding ammonia water with the concentration of 25% into an ammonium dimolybdate aqueous solution, wherein the reaction temperature is 70 ℃, and the pH value is 6.8, so as to obtain an ammonium molybdate solution; evaporating and concentrating the ammonium molybdate solution, and controlling the density of the ammonium molybdate solution to be 1.36g/cm3Obtaining ammonium heptamolybdate solution with the pH value of 6.3; filtering the ammonium heptamolybdate solution to remove impurities; and (2) injecting the filtered and impurity-removed ammonium heptamolybdate solution into a cooling crystallizer for cooling crystallization, wherein the injection volume amount is 75% of the full liquid level of the cooling crystallizer, the stirring speed is controlled to be 120r/min in the cooling crystallization process, the crystallization temperature is 22 ℃, feeding is started continuously and discharging is started at intervals after crystals are separated out, the interval time of discharging at intervals is 15min, the discharged liquid is filtered to obtain a crystallized filter cake, and then the crystallized filter cake is subjected to centrifugal drying and drying in sequence to obtain an ammonium heptamolybdate product.
The ammonium heptamolybdate product obtained in this example had a nitrate impurity content of 18.6ppm, a solubility in pure water at 25 ℃ of 61g/100ml, and a particle size of 409.8 μm.
Example 2
Taking ammonium dimolybdate in mass ratio: deionized water 1:1 ammonium dimolybdate aqueous solution, wherein the mass percent of molybdenum in the ammonium dimolybdate is 56.21%; adding ammonia water with the concentration of 25% into an ammonium dimolybdate aqueous solution, wherein the reaction temperature is 70 ℃, and the pH value is 7.2, so as to obtain an ammonium molybdate solution; evaporating and concentrating the ammonium molybdate solution, and controlling the density of the ammonium molybdate solution to be 1.4g/cm3Obtaining ammonium heptamolybdate solution with the pH value of 6.8; filtering the ammonium heptamolybdate solution to remove impurities; and (2) injecting the filtered and impurity-removed ammonium heptamolybdate solution into a cooling crystallizer for cooling crystallization, wherein the injection volume amount is 80% of the full liquid level of the cooling crystallizer, the stirring speed is controlled at 130r/min in the cooling crystallization process, the crystallization temperature is 20 ℃, feeding is started continuously and discharging is started at intervals after crystals are separated out, the interval time of discharging at intervals is 15min, a crystal filter cake is obtained by filtering the discharged liquid, and then, the crystal filter cake is sequentially subjected to centrifugal drying and drying to obtain the ammonium heptamolybdate product.
The ammonium heptamolybdate product obtained in this example had a nitrate impurity content of 19.1ppm, a solubility in pure water at 25 ℃ of 63g/100ml, and a product particle size of 406.5. mu.m.
Example 3
Taking ammonium dimolybdate in mass ratio: 1:1 deionized water, wherein the mass percent of molybdenum in the ammonium dimolybdate is 56.24%; adding ammonia water with the concentration of 25% into an ammonium dimolybdate aqueous solution, wherein the reaction temperature is 70 ℃, and the pH value is 7.0, so as to obtain an ammonium molybdate solution; evaporating and concentrating the ammonium molybdate solution, and controlling the density of the ammonium molybdate solution to be 1.38g/cm3Obtaining ammonium heptamolybdate solution with the pH value of 6.5; filtering the ammonium heptamolybdate solution to remove impurities; injecting the filtered and impurity-removed ammonium heptamolybdate solution into a cooling crystallizer for cooling crystallization, wherein the injection volume is 76% of the full liquid level of the cooling crystallizer, the stirring speed is controlled at 124r/min, the crystallization temperature is 21 ℃, after crystals are precipitated, continuous feeding and intermittent discharging are started, the intermittent discharging time is 15min, filtering the discharged liquid to obtain a crystallized filter cake, and then sequentially carrying out centrifugal spin-drying, and the like on the crystallized filter cake,Drying to obtain the ammonium heptamolybdate product.
The ammonium heptamolybdate product obtained in this example had a nitrate impurity content of 19.3ppm, a solubility in pure water at 25 ℃ of 62g/100ml, and a particle size of 408.7 μm.
Example 4
Taking ammonium dimolybdate in mass ratio: 1:1 deionized water, wherein the mass percent of molybdenum in the ammonium dimolybdate is 56.23%; adding ammonia water with the concentration of 25% into an ammonium dimolybdate aqueous solution, wherein the reaction temperature is 70 ℃, and the pH value is 6.9, so as to obtain an ammonium molybdate solution; evaporating and concentrating the ammonium molybdate solution, and controlling the density of the ammonium molybdate solution to be 1.37g/cm3Obtaining ammonium heptamolybdate solution with the pH value of 6.4; filtering the ammonium heptamolybdate solution to remove impurities; and (2) injecting the filtered and impurity-removed ammonium heptamolybdate solution into a cooling crystallizer for cooling crystallization, wherein the injection volume is 78% of the full liquid level of the cooling crystallizer, the stirring speed is controlled at 123r/min, the crystallization temperature is 22 ℃, feeding is started continuously and discharging is started at intervals after crystals are separated out, the interval time of discharging at intervals is 15min, a crystal filter cake is obtained by filtering the discharged liquid, and then, the crystal filter cake is sequentially subjected to centrifugal drying and drying to obtain an ammonium heptamolybdate product.
The ammonium heptamolybdate product obtained in this example had a nitrate impurity content of 18.5ppm, a solubility in pure water at 25 ℃ of 61g/100ml, and a particle size of 408.8 μm.
Example 5
Taking ammonium dimolybdate in mass ratio: deionized water 1:1 ammonium dimolybdate aqueous solution, wherein the mass percent of molybdenum in the ammonium dimolybdate is 56%; adding ammonia water with the concentration of 25% into an ammonium dimolybdate aqueous solution, wherein the reaction temperature is 70 ℃, and the pH value is 7.1 to obtain an ammonium molybdate solution; evaporating and concentrating the ammonium molybdate solution, and controlling the density of the ammonium molybdate solution to be 1.39g/cm3Obtaining ammonium heptamolybdate solution with the pH value of 6.7; filtering the ammonium heptamolybdate solution to remove impurities; injecting the filtered and impurity-removed ammonium heptamolybdate solution into a cooling crystallizer for cooling crystallization, wherein the injection volume is 79 percent of the full liquid level of the cooling crystallizer, the stirring speed is controlled to be 126r/min in the cooling crystallization process, the crystallization temperature is 22 ℃, and after crystals are separated out, continuous feeding is started and intermittent feeding is carried outAnd discharging at intervals, wherein the interval time of the discharging at intervals is 15min, filtering the discharged liquid to obtain a crystallized filter cake, and then sequentially carrying out centrifugal drying and drying on the crystallized filter cake to obtain an ammonium heptamolybdate product.
The ammonium heptamolybdate product obtained in this example had a nitrate impurity content of 19.2ppm, a solubility in pure water at 25 ℃ of 63g/100ml, and a particle size of 407.9 μm.
Claims (10)
1. A continuous preparation method of ammonium heptamolybdate is characterized by comprising the following steps:
step 1, dissolving: adding ammonia water into an ammonium dimolybdate aqueous solution to obtain an ammonium molybdate solution;
step 2, concentration: evaporating and concentrating the ammonium molybdate solution obtained in the step 1 to obtain an ammonium heptamolybdate solution;
and step 3, filtering: filtering and removing impurities from the ammonium heptamolybdate solution obtained in the step 2;
and 4, cooling and crystallizing: and (3) injecting the ammonium heptamolybdate solution filtered and purified in the step (3) into a cooling crystallizer for cooling crystallization, starting continuous feeding and discharging at intervals after crystals are separated out, filtering the discharged liquid to obtain a crystallized filter cake, and then sequentially carrying out centrifugal drying and drying on the crystallized filter cake to obtain an ammonium heptamolybdate product.
2. The continuous preparation method of ammonium heptamolybdate according to claim 1, wherein the mass ratio of ammonium dimolybdate to deionized water in the ammonium dimolybdate aqueous solution of step 1 is 1: 1.
3. the continuous production method of ammonium heptamolybdate according to claim 2, wherein the mass percentage of molybdenum in the ammonium dimolybdate is not less than 56%.
4. The continuous production method of ammonium heptamolybdate according to claim 1, wherein the concentration of the aqueous ammonia in step 1 is 25%.
5. The continuous method of preparing ammonium heptamolybdate according to claim 1, wherein the temperature of the reaction of the aqueous solution of ammonium dimolybdate with ammonia in step 1 is 70 ℃ and the pH is 6.8 to 7.2.
6. The continuous method for preparing ammonium heptamolybdate according to claim 1, wherein the concentration of ammonium molybdate solution in the evaporation concentration process of step 2 is controlled to be 1.36-1.4g/cm3The pH value is 6.3-6.8.
7. The continuous method for preparing ammonium heptamolybdate according to claim 1, wherein the volume of the ammonium heptamolybdate solution injected into the cooling crystallizer in the step 4 is 75-80% of the full level of the cooling crystallizer.
8. The continuous preparation method of ammonium heptamolybdate according to claim 1, wherein the stirring speed is controlled to be 120-130r/min during the temperature-reducing crystallization process of step 4, and the crystallization temperature is not higher than 22 ℃.
9. The method for continuously preparing ammonium heptamolybdate according to claim 1, wherein the time interval between the discharging in step 4 is 15 min.
10. The method of claim 1, wherein the cooling crystallizer used in step 4 is a QJ cooling crystallizer made of 316 stainless steel.
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Cited By (2)
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| CN114195192A (en) * | 2021-12-15 | 2022-03-18 | 成都虹波钼业有限责任公司 | Ammonium heptamolybdate and production process thereof |
| CN115611313A (en) * | 2022-12-12 | 2023-01-17 | 中南大学 | Process for producing ammonium paramolybdate tetrahydrate |
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Cited By (2)
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| CN114195192A (en) * | 2021-12-15 | 2022-03-18 | 成都虹波钼业有限责任公司 | Ammonium heptamolybdate and production process thereof |
| CN115611313A (en) * | 2022-12-12 | 2023-01-17 | 中南大学 | Process for producing ammonium paramolybdate tetrahydrate |
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