CN109081374B - Method for preparing large-particle-size spherical ammonium polyvanadate - Google Patents
Method for preparing large-particle-size spherical ammonium polyvanadate Download PDFInfo
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Abstract
The invention relates to a method for preparing large-particle-size spherical ammonium polyvanadate, which comprises the following steps: adding the vanadium-containing purified liquid into a crystallizer, controlling the heating rate to be 0.1-3 ℃/h, heating the vanadium-containing purified liquid to 85-95 ℃, adding ammonium salt in the heating process, and adjusting the pH value; continuously adding the vanadium-containing purification solution into a crystallizer after the temperature of the vanadium-containing purification solution reaches a preset value, controlling the heating rate to be 6-10 ℃/h, keeping the temperature of the vanadium-containing purification solution at 85-95 ℃, adding ammonium salt and adjusting the pH value in the heating process, and crystallizing to obtain spherical ammonium polyvanadate with the particle size of more than 150 mu m. The spherical ammonium polyvanadate with the granularity of more than 150 mu m is prepared, the sphericity of the obtained ammonium polyvanadate product is high, the particle strength is high, the requirement of the field of vanadium alloy and vanadium electrolyte on the granularity of a vanadium pentoxide product can be met, and the method has a good application prospect.
Description
Technical Field
The invention relates to the field of vanadium chemical industry, in particular to a method for preparing large-particle-size spherical ammonium polyvanadate.
Background
Vanadium has excellent strength, ductility and heat resistance, can obviously improve the performance of steel, is an indispensable important element for producing high-strength steel, and is called monosodium glutamate in modern industry.
The vanadium pentoxide obtained by the traditional ammonium salt vanadium precipitation method has small particle size which is generally below 80 mu m, and the vanadium pentoxide with small particle size has weak wettability and poor airflow transportability, thus being incapable of meeting the production requirements of vanadium electrolytes with different valence states in the field of energy storage. In addition, the vanadium pentoxide with small particle size is adopted as a raw material to prepare the vanadium alloy, so that serious gas and material flying can be inevitably caused, and the smelting loss of expensive vanadium oxide can be caused by entrainment overflowing from furnace gas. Ammonium polyvanadate is an important raw material for preparing vanadium pentoxide, so that increasing the particle size of ammonium polyvanadate is one of important means for obtaining vanadium pentoxide with large particle size.
CN104760996A discloses a method for crystallizing ammonium polyvanadate at low temperature, which comprises adding a seeding agent into a vanadium liquid, stirring and dissolving; then adding acid to adjust the pH value of the vanadium liquid to 1.0-7.0; continuously stirring to separate out ammonium polyvanadate crystals, and filtering to obtain ammonium polyvanadate crystals; the seeding agent is one or a mixture of a plurality of water-soluble organic amines and derivatives thereof. The obtained ammonium polyvanadate crystal has small grain size and is difficult to meet the requirement of preparing large-grain vanadium pentoxide.
CN1258642A discloses a method for preparing spherical ammonium polyvanadate by continuously adding ammonium sulfate, but the method is difficult to control the addition of ammonium sulfate, and requires additional automatic control equipment, thereby increasing the investment cost.
CN102502823A discloses a preparation method of ammonium polyvanadate with high tap density, which comprises the following steps: a) adding ammonium polyvanadate seed crystal and ammonium sulfate under the conditions that the pH of the vanadium-containing liquid is 5.0-5.5 and the temperature is 60-90 ℃; b) b, adjusting the pH value of the vanadium-containing liquid obtained in the step a to 2.2-2.4, raising the temperature of the vanadium-containing liquid to 90-95 ℃, and precipitating ammonium polyvanadate under rapid stirring; c) b, adding ammonium sulfate twice to the vanadium-containing liquid obtained in the step b, and reducing the stirring speed to precipitate ammonium polyvanadate; d) and filtering, washing and drying to obtain the ammonium polyvanadate with high tap density, wherein the method needs to add acid step by step and is complex to operate.
The ammonium polyvanadate obtained by the method has unsatisfactory granularity, needs additional external equipment and is not beneficial to large-scale popularization. Therefore, it is necessary to develop a method for preparing ammonium polyvanadate with large particle size to meet the demand of vanadium pentoxide product particle size in the fields of vanadium alloy, vanadium electrolyte and the like.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for preparing large-granularity spherical ammonium polyvanadate, which solves the problem of small ammonium polyvanadate crystal granularity under natural conditions, the prepared ammonium polyvanadate has granularity of more than 150 μm, high sphericity and high particle strength, and can meet the requirement of vanadium pentoxide product granularity in the fields of vanadium alloy and vanadium electrolyte; and the equipment has high automation degree, the process operation is simple, the industrial production is facilitated, and the method has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing large-particle-size spherical ammonium polyvanadate, which comprises the following steps of:
(1) adding the vanadium-containing purified liquid into a crystallizer, controlling the heating rate to be 0.1-3 ℃/h, heating the vanadium-containing purified liquid to 85-95 ℃, adding ammonium salt in the heating process, and adjusting the pH value;
(2) and (2) after the temperature of the vanadium-containing purification solution in the step (1) reaches 85-95 ℃, continuously adding the vanadium-containing purification solution into a crystallizer, controlling the heating rate to be 6-10 ℃/h, keeping the temperature of the vanadium-containing purification solution at 85-95 ℃, adding ammonium salt and adjusting the pH in the heating process, and crystallizing to obtain spherical ammonium polyvanadate with the particle size of more than 150 mu m.
The invention realizes the preparation of large-particle-size spherical ammonium polyvanadate (larger than 150 mu m) by controlling the parameters of the crystallization process. Wherein, the temperature is firstly increased at 0.1-3 ℃/h, and at the rate, the ammonium polyvanadate generated by the reaction can form a larger crystal nucleus; subsequently, the heating rate is increased to 6-10 ℃/h, which is beneficial to quickly agglomerating newly generated ammonium polyvanadate around the previously formed crystal nucleus, and further spherical ammonium polyvanadate with the granularity of more than 150 mu m is obtained.
According to the invention, the temperature increase rate of the crystallizer in step (1) is controlled to be 0.1-3 ℃/h, for example, 0.1 ℃/h, 0.5 ℃/h, 1 ℃/h, 1.5 ℃/h, 2 ℃/h, 2.5 ℃/h or 3 ℃/h, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
When the temperature rise rate in the step (1) is too slow (less than 0.1 ℃/h), the crystallization time is too long, generated crystal nuclei are already separated out, the ammonium polyvanadate with large particle size is difficult to obtain subsequently, and the production efficiency is reduced; when the temperature rise rate is too fast (more than 3 ℃/h), the number of large crystal nuclei is reduced, which is not beneficial to preparing the ammonium polyvanadate with large particle size.
According to the invention, the temperature rise rate of the crystallizer in the step (2) is controlled to be 6-10 ℃/h, for example, 6 ℃/h, 6.5 ℃/h, 7 ℃/h, 7.5 ℃/h, 8 ℃/h, 8.5 ℃/h, 9 ℃/h, 9.5 ℃/h or 10 ℃/h, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive.
When the temperature rise rate in the step (2) is too slow (less than 6 ℃/h), the agglomeration rate of the ammonium polyvanadate is slowed, and the preparation of the ammonium polyvanadate with large particle size is not facilitated; when the temperature rise rate is too fast (more than 10 ℃/h), the heat distribution is not uniform due to the too fast temperature rise, and the obtained ammonium polyvanadate product has irregular shape and is not beneficial to subsequent application.
According to the invention, the temperature of the vanadium-containing purified liquid in the crystallizer in the step (1) is raised to 85-95 ℃, for example, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃ or 95 ℃, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the pH of the vanadium-containing purified liquid in the step (1) is controlled to be 1.9-2.3, for example, 1.9, 2, 2.1, 2.2 or 2.3, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the present invention, the temperature of the vanadium-containing purified liquid in the crystallizer in the step (2) is controlled to be 85-95 ℃, for example, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃ or 95 ℃, and the specific values between the above values are limited by space and for the sake of brevity, and the present invention is not exhaustive.
According to the invention, the pH of the vanadium-containing purified liquid in the step (2) is controlled to be 1.9-2.3, for example, 1.9, 2, 2.1, 2.2 or 2.3, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the concentration of vanadium in the vanadium-containing purification solution is 20-40g/L, for example, 20g/L, 23g/L, 25g/L, 28g/L, 30g/L, 33g/L, 35g/L, 38g/L or 40g/L, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the crystallizer is an OSLO crystallizer or a DTB crystallizer.
According to the invention, the ammonium salt is ammonium sulfate.
According to the invention, during the addition of the ammonium salt, NH in the ammonium salt is controlled4 +And the molar ratio of V in the vanadium-containing purified liquor is (0.7-1.0):1, and may be, for example, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1 or 1.0:1, and the specific values therebetween, are not exhaustive for reasons of brevity and brevity.
According to the invention, the heating rate of the solution in the crystallizer is controlled by adjusting the hot water flow and the frequency of the circulating pump through the hot water pump.
According to the invention, the temperature difference between the backwater of the crystallizer heating water and the solution in the crystallizer is controlled to be less than or equal to 5 ℃ in the whole crystallization process, and when the temperature difference between the backwater of the crystallizer heating water and the solution in the crystallizer is more than 5 ℃, the heat exchanger is easy to be scabbed at a heat exchange interface (the wall of the heat exchanger tube) to cause the blockage of the heat.
According to the invention, sulfuric acid is added during the crystallization to adjust the pH of the solution.
According to the invention, the liquid level in the crystallizer is controlled to reach the overflow port in the step (1), and the liquid level in the crystallizer is controlled to be higher than the overflow port in the step (2).
According to the invention, spherical ammonium polyvanadate obtained by crystallization in a crystallizer is filtered, washed and dried.
According to the invention, the flow rate of the vanadium-containing purification liquid controlled by the feed pump in the step (2) is 0.1-10m3And h, correspondingly adjusting the frequency of the discharging pump to enable the liquid level in the crystallizer to be higher than the overflow port so as to ensure that the feeding and discharging are balanced.
As a preferred technical solution, the method for preparing large-particle spherical ammonium polyvanadate according to the present invention comprises the following steps:
(1) starting a feed pump, adding the vanadium-containing purified liquid with the vanadium concentration of 20-40g/L into the crystallizer until the liquid level reaches an overflow port;
(2) starting a heating water pump and a circulating pump, controlling the heating rate to be 0.1-3 ℃/h, and heating the vanadium-containing purification solution in the crystallizer to 85-95 ℃; controlling the temperature difference between the backwater of the heated water in the crystallizer and the solution in the crystallizer to be less than or equal to 5 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of (0.7-1.0) to 1 in the temperature rising process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 1.9-2.3;
(3) after the temperature of the vanadium-containing purification solution in the crystallizer reaches 85-95 ℃, starting a feed pump to continuously add the vanadium-containing purification solution into the crystallizer, controlling the heating rate to be 6-10 ℃/h, keeping the temperature of the vanadium-containing purification solution at 85-95 ℃, controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 5 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of (0.7-1.0) to 1 in the heating process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 1.9-2.3; starting a discharging pump to discharge, and controlling the liquid level in the crystallizer to be higher than an overflow port;
(4) after the material is discharged by a discharge pump, spherical ammonium polyvanadate with the granularity of more than 150 mu m is obtained after filtering, washing and drying.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the invention, spherical ammonium polyvanadate with the granularity of more than 150 μm is prepared by controlling the parameters of the crystallization process, the obtained ammonium polyvanadate product has high sphericity and high particle strength, and can meet the requirements of the vanadium alloy and vanadium electrolyte field on the granularity of the vanadium pentoxide product;
(2) the invention has high automation degree of equipment and simple process operation, is beneficial to industrial production and has good application prospect.
Drawings
Fig. 1 is a schematic structural diagram of a crystallizer according to an embodiment of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The method for preparing large-particle-size spherical ammonium polyvanadate provided by a specific embodiment of the invention can be carried out by adopting the crystallizer provided in FIG. 1. In the preparation process, firstly, adding the solution in an ammonium polyvanadate solution buffer tank into a crystallizer through a feed pump until the liquid level reaches an overflow port; then starting a heating water pump and a circulating pump, controlling the temperature of the solution in the crystallizer by adjusting the flow rate of hot water and the frequency of the circulating pump, adding the solution in an ammonium sulfate solution tank into the crystallizer in the temperature rising process, and simultaneously adding sulfuric acid to adjust the pH value of the solution; and after the temperature of the vanadium-containing purification liquid in the crystallizer reaches a preset value, starting a feed pump to continuously add the vanadium-containing purification liquid into the crystallizer, controlling the temperature of the solution in the crystallizer, simultaneously adding ammonium sulfate and sulfuric acid, starting a discharge pump to discharge, controlling the liquid level in the crystallizer to be higher than an overflow port and the temperature difference between the water heated by the crystallizer and the solution in the crystallizer to be less than or equal to 5 ℃ in the crystallization process, filtering, washing and drying the discharged material by the discharge pump to obtain spherical ammonium polyvanadate with the particle size of more than 150 mu m.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
(1) Starting a feed pump, and adding a vanadium purification solution with the vanadium concentration of 30.12g/L into the crystallizer until the liquid level reaches an overflow port;
(2) starting a heating water pump and a circulating pump, controlling the heating rate of the crystallizer to be 1 ℃ by adjusting the hot water flow and the frequency of the circulating pump, and heating the vanadium-containing purification liquid in the crystallizer to 90 ℃; controlling the temperature difference between the backwater of the heated water in the crystallizer and the solution in the crystallizer to be less than or equal to 2 ℃, slowly adding ammonium sulfate according to the ammonium-vanadium molar ratio of 0.8:1 in the temperature rising process, and simultaneously slowly adding sulfuric acid to adjust the pH value of the solution to be 2;
(3) after the temperature of the vanadium-containing purification liquid in the crystallizer reaches 90 ℃, starting a feed pump to continuously add the vanadium-containing purification liquid into the crystallizer, wherein the feed flow is 8m3Controlling the heating rate to be 8 ℃/h, keeping the temperature of the vanadium-containing purification solution at 90 ℃, controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 2 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of 0.8:1 in the heating process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 2; starting a discharging pump to discharge, and controlling the liquid level in the crystallizer to be higher than an overflow port;
(4) after the material is discharged by a discharge pump, spherical ammonium polyvanadate with the granularity of more than 150 mu m is obtained after filtering, washing and drying.
Through detection: the obtained ammonium polyvanadate product has the content of 70 wt% with the particle size larger than 150 mu m and smaller than 300 mu m and the content of 30 wt% with the particle size larger than or equal to 300 mu m.
Example 2
(1) Starting a feed pump, and adding a vanadium purification liquid with the vanadium concentration of 35.64g/L into the crystallizer until the liquid level reaches an overflow port;
(2) starting a heating water pump and a circulating pump, controlling the temperature rise rate of the crystallizer to be 2 ℃ by adjusting the hot water flow and the frequency of the circulating pump, and raising the temperature of the vanadium-containing purification liquid in the crystallizer to 85 ℃; controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 4 ℃, slowly adding ammonium sulfate according to the ammonium-vanadium molar ratio of 0.9:1 in the temperature rising process, and simultaneously slowly adding sulfuric acid to adjust the pH value of the solution to be 2.2;
(3) after the temperature of the vanadium-containing purification liquid in the crystallizer reaches 85 ℃, starting a feed pump to continuously add the vanadium-containing purification liquid into the crystallizer, wherein the feed flow is 4m3Controlling the heating rate to be 6 ℃/h, keeping the temperature of the vanadium-containing purification solution at 85 ℃, controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 4 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of 0.9:1 in the heating process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 2.2; starting a discharging pump to discharge, and controlling the liquid level in the crystallizer to be higher than an overflow port;
(4) after the material is discharged by a discharge pump, spherical ammonium polyvanadate with the granularity of more than 150 mu m is obtained after filtering, washing and drying.
Through detection: the obtained ammonium polyvanadate product has the content of 63 wt% with the particle size larger than 150 mu m and smaller than 300 mu m and the content of 37 wt% with the particle size larger than or equal to 300 mu m.
Example 3
(1) Starting a feed pump, and adding a vanadium purification liquid with the vanadium concentration of 24.95g/L into the crystallizer until the liquid level reaches an overflow port;
(2) starting a heating water pump and a circulating pump, controlling the temperature rise rate of the crystallizer to be 3 ℃ by adjusting the hot water flow and the frequency of the circulating pump, and raising the temperature of the vanadium-containing purification liquid in the crystallizer to 88 ℃; controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 5 ℃, slowly adding ammonium sulfate according to the ammonium-vanadium molar ratio of 1:1 in the temperature rising process, and simultaneously slowly adding sulfuric acid to adjust the pH value of the solution to be 1.9;
(3) in the mold to be crystallizedAfter the temperature of the vanadium-containing purification liquid reaches 88 ℃, starting a feed pump to continuously add the vanadium-containing purification liquid into the crystallizer, wherein the feed flow is 1m3Controlling the heating rate to be 9 ℃/h, keeping the temperature of the vanadium-containing purification solution at 88 ℃, controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 4 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of 1:1 in the heating process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 1.9; starting a discharging pump to discharge, and controlling the liquid level in the crystallizer to be higher than an overflow port;
(4) after the material is discharged by a discharge pump, spherical ammonium polyvanadate with the granularity of more than 150 mu m is obtained after filtering, washing and drying.
Through detection: the obtained ammonium polyvanadate product has the content of 68 wt% with the particle size larger than 150 mu m and smaller than 300 mu m, and the content of 32 wt% with the particle size larger than or equal to 300 mu m.
Example 4
(1) Starting a feed pump, and adding a vanadium purification solution with the vanadium concentration of 20.31g/L into the crystallizer until the liquid level reaches an overflow port;
(2) starting a heating water pump and a circulating pump, controlling the temperature rise rate of the crystallizer to be 0.5 ℃ by adjusting the hot water flow and the frequency of the circulating pump, and raising the temperature of the vanadium-containing purification liquid in the crystallizer to 92 ℃; controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 2 ℃, slowly adding ammonium sulfate according to the ammonium-vanadium molar ratio of 0.75:1 in the temperature rising process, and simultaneously slowly adding sulfuric acid to adjust the pH value of the solution to be 2.3;
(3) after the temperature of the vanadium-containing purification liquid in the crystallizer reaches 92 ℃, starting a feed pump to continuously add the vanadium-containing purification liquid into the crystallizer, wherein the feed flow is 1.5m3Controlling the heating rate to be 10 ℃/h, keeping the temperature of the vanadium-containing purification solution at 95 ℃, controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 3 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of 0.8:1 in the heating process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 2.0; starting a discharging pump to discharge, and controlling the liquid level in the crystallizer to be higher than an overflow port;
(4) after the material is discharged by a discharge pump, spherical ammonium polyvanadate with the granularity of more than 150 mu m is obtained after filtering, washing and drying.
Through detection: the obtained ammonium polyvanadate product has the content of 62 wt% with the particle size larger than 150 mu m and smaller than 300 mu m, and the content of 38 wt% with the particle size larger than or equal to 300 mu m.
Example 5
(1) Starting a feed pump, and adding vanadium purification liquid with vanadium concentration of 39.41g/L into the crystallizer until the liquid level reaches an overflow port;
(2) starting a heating water pump and a circulating pump, controlling the heating rate of the crystallizer to be 1.5 ℃ by adjusting the hot water flow and the frequency of the circulating pump, and heating the vanadium-containing purification liquid in the crystallizer to 95 ℃; controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 3 ℃, slowly adding ammonium sulfate according to the ammonium-vanadium molar ratio of 0.9:1 in the temperature rising process, and simultaneously slowly adding sulfuric acid to adjust the pH value of the solution to be 2.1;
(3) after the temperature of the vanadium-containing purification liquid in the crystallizer reaches 95 ℃, starting a feed pump to continuously add the vanadium-containing purification liquid into the crystallizer, wherein the feed flow is 9m3Controlling the heating rate to be 7 ℃/h, keeping the temperature of the vanadium-containing purification solution at 91 ℃, controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 3 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of 0.85:1 in the heating process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 2.1; starting a discharging pump to discharge, and controlling the liquid level in the crystallizer to be higher than an overflow port;
(4) after the material is discharged by a discharge pump, spherical ammonium polyvanadate with the granularity of more than 150 mu m is obtained after filtering, washing and drying.
Through detection: the obtained ammonium polyvanadate product has the content of 66 wt% with the particle size larger than 150 μm and smaller than 300 μm, and the content of 34 wt% with the particle size larger than or equal to 300 μm.
Comparative example 1
The procedure and conditions were exactly the same as those in example 1 except that the temperature increase rate of the crystallizer in step (2) was adjusted to 0.05 ℃/h as compared with example 1.
The result shows that the crystallization time is too long, the generated crystal nucleus is separated out, and the particle size of the ammonium metavanadate product obtained subsequently is generally less than or equal to 150 mu m.
Comparative example 2
The procedure and conditions were exactly the same as in example 1 except that the temperature increase rate of the crystallizer in step (2) was adjusted to 4 ℃ as compared with example 1.
Through detection: the content of the ammonium polyvanadate product with the particle size of less than or equal to 150 mu m is 31 percent, the content of the ammonium polyvanadate product with the particle size of more than 150 mu m and less than 300 mu m is 66 weight percent, and the content of the ammonium polyvanadate product with the particle size of more than or equal to 300 mu m is 3 weight percent.
Comparative example 3
The procedure and conditions were exactly the same as in example 1 except that the temperature increase rate of the crystallizer in step (3) was adjusted to 4 ℃ as compared with example 1.
Through detection: the content of the ammonium polyvanadate product with the particle size of less than or equal to 150 mu m is 23 percent, the content of the ammonium polyvanadate product with the particle size of more than 150 mu m and less than 300 mu m is 72 percent by weight, and the content of the ammonium polyvanadate product with the particle size of more than or equal to 300 mu m is 5 percent by weight.
Comparative example 4
The procedure and conditions were exactly the same as in example 1 except that the temperature increase rate of the crystallizer in step (3) was adjusted to 12 ℃ as compared with example 1.
Through detection: the obtained ammonium polyvanadate product has spherical, elliptical, polygonal and the like, and is irregular in shape, so that the application performance of the product is influenced.
Comparative example 5
Compared with the example 1, the steps and conditions are completely the same as the example 1 except that the temperature difference between the backwater of the crystallizer heating water and the solution in the crystallizer in the step (3) is 6 ℃.
The results show that scarring on the tube wall blocks the tube, affecting the progress of crystallization.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. A method for preparing large-particle-size spherical ammonium polyvanadate, which is characterized by comprising the following steps of:
(1) adding the vanadium-containing purified liquid into a crystallizer, controlling the heating rate to be 0.1-3 ℃/h, heating the vanadium-containing purified liquid to 85-95 ℃, adding ammonium salt in the heating process, and adjusting the pH value;
(2) continuously adding the vanadium-containing purification solution into a crystallizer after the temperature of the vanadium-containing purification solution in the step (1) reaches 85-95 ℃, controlling the heating rate to be 6-10 ℃/h, keeping the temperature of the vanadium-containing purification solution at 85-95 ℃, adding ammonium salt and adjusting the pH in the heating process, and crystallizing to obtain spherical ammonium polyvanadate with the particle size of more than 150 mu m;
in the process of adding the ammonium salt, NH in the ammonium salt is controlled4 +And the mol ratio of V in the vanadium-containing purification solution is (0.7-1.0) to 1;
the temperature difference between the backwater of the heating water of the crystallizer and the solution in the crystallizer is controlled to be less than or equal to 5 ℃ in the whole crystallization process.
2. The method of claim 1, wherein the concentration of vanadium in the vanadium-containing purified liquor is 20-40 g/L.
3. The method according to claim 1 or 2, wherein the crystallizer is an OSLO crystallizer or a DTB crystallizer.
4. The method of claim 1 or 2, wherein the ammonium salt is ammonium sulfate.
5. The method of claim 1 or 2, wherein the pH of the solution is adjusted to 1.9 to 2.3 in step (1) and step (2) by adding sulfuric acid.
6. The method of claim 1 or 2, wherein the liquid level in the crystallizer is controlled to reach the overflow port in step (1).
7. The method of claim 6, wherein the liquid level in the crystallizer is controlled to be higher than the overflow port in the step (2).
8. The method according to claim 1 or 2, wherein spherical ammonium polyvanadate crystallized in the crystallizer is filtered, washed and dried.
9. The method of claim 1, wherein the method comprises the steps of:
(1) starting a feed pump, adding the vanadium-containing purified liquid with the vanadium concentration of 20-40g/L into the crystallizer until the liquid level reaches an overflow port;
(2) starting a heating water pump and a circulating pump, controlling the heating rate to be 0.1-3 ℃/h, and heating the vanadium-containing purification solution in the crystallizer to 85-95 ℃; controlling the temperature difference between the backwater of the heated water in the crystallizer and the solution in the crystallizer to be less than or equal to 5 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of (0.7-1.0) to 1 in the temperature rising process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 1.9-2.3;
(3) after the temperature of the vanadium-containing purification solution in the crystallizer reaches 85-95 ℃, starting a feed pump to continuously add the vanadium-containing purification solution into the crystallizer, controlling the heating rate to be 6-10 ℃/h, keeping the temperature of the vanadium-containing purification solution at 85-95 ℃, controlling the temperature difference between the heated backwater of the crystallizer and the solution in the crystallizer to be less than or equal to 5 ℃, adding ammonium sulfate according to the ammonium-vanadium molar ratio of (0.7-1.0) to 1 in the heating process, and simultaneously adding sulfuric acid to adjust the pH value of the solution to be 1.9-2.3; starting a discharging pump to discharge, and controlling the liquid level in the crystallizer to be higher than an overflow port;
(4) after the material is discharged by a discharge pump, spherical ammonium polyvanadate with the granularity of more than 150 mu m is obtained after filtering, washing and drying.
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