CN114349050B - Method for preparing high-purity molybdic acid from calcium molybdate - Google Patents
Method for preparing high-purity molybdic acid from calcium molybdate Download PDFInfo
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Abstract
The invention provides a method for preparing high-purity molybdic acid from calcium molybdate, which comprises the following steps: s1, adding a leaching solvent into calcium molybdate serving as a raw material to obtain a sodium molybdate leaching solution; s2, carrying out gas stripping deamination on the sodium molybdate leaching solution obtained in the step S1 to obtain a deaminated molybdenum-containing solution; s3, adding hydrogen peroxide into the deamination molybdenum-containing solution obtained in the step S2 for oxidation reaction to obtain an intermediate reaction solution; s4, adding nitric acid into the intermediate reaction liquid obtained in the step S3 to adjust the pH value, heating for reaction, and separating out molybdic acid crystals; and S5, filtering out the molybdic acid crystals obtained in the step S4, washing and drying to obtain high-purity molybdic acid.
Description
Technical Field
The invention relates to the field of catalyst production, in particular to a method for preparing high-purity molybdic acid from calcium molybdate.
Background
High-purity molybdic acid is a new product which has been recently developed, and since it is an acid anhydride of molybdenum trioxide, its composition is almost the same as that of high-purity molybdenum trioxide, and its composition can be understood as a composition of one molybdenum trioxide molecule plus one molecule of water. Therefore, the molybdenum trioxide has the effect of isoqu in physical and chemical properties with high purity molybdenum trioxide. Research on the physical properties of molybdic acid shows that molybdic acid is a weak acid, the loss of anhydride crystal water requires less energy, and molybdenum trioxide can be easily formed, and the research shows that the crystal water in molybdic acid can be lost by more than 95% at 150 ℃.
From the processing process of molybdic acid, the processing of common molybdic acid is simpler, and the method of acidifying molybdate solution is adopted, but the molybdic acid produced in the method has high impurity content and cannot meet the requirement of the industry on high-purity molybdic acid.
Disclosure of Invention
The present invention provides a method for preparing high-purity molybdic acid from calcium molybdate, which can effectively solve the above problems.
The invention provides a method for preparing high-purity molybdic acid from calcium molybdate, which comprises the following steps:
s1, adding a leaching solvent into calcium molybdate serving as a raw material to obtain a sodium molybdate leaching solution;
s2, carrying out gas stripping deamination on the sodium molybdate leaching solution obtained in the step S1 to obtain a deaminated molybdenum-containing solution;
s3, adding hydrogen peroxide into the deamination molybdenum-containing solution obtained in the step S2 for oxidation reaction to obtain an intermediate reaction solution;
s4, adding nitric acid into the intermediate reaction liquid obtained in the step S3 to adjust the pH value, heating for reaction, and separating out molybdic acid crystals;
and S5, filtering out the molybdic acid crystals obtained in the step S4, washing and drying to obtain high-purity molybdic acid.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects:
according to the method for preparing high-purity molybdic acid from calcium molybdate, calcium molybdate is used as a raw material, sodium carbonate or sodium dihydrogen phosphate is used for leaching to obtain a sodium molybdate solution, sodium hydroxide leaching is replaced, and the cost is reduced; aiming at the problem of ammonia in the solution, the invention adopts gas stripping deamination, the consumption of sodium hydroxide is low, the deamination depth is high, and the process is simple; the problems of complex flow and high consumption of the prior art are solved; adding low-valence molybdenum in the dicationic water oxidation solution into the deamination solution to avoid the formation of a molybdic acid impurity phase under an acidic condition and improve the granularity of a product; the molybdic acid particles prepared by the method are in a loose chrysanthemum shape, have excellent solubility and can be quickly dissolved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a first scanning electron micrograph of high-purity molybdic acid according to example 1 of the present invention;
FIG. 2 is a second scanning electron micrograph of the highly pure molybdic acid provided in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The specific embodiment provides a method for preparing high-purity molybdic acid from calcium molybdate, which comprises the following steps:
s1, adding a leaching solvent into calcium molybdate serving as a raw material to obtain a sodium molybdate leaching solution;
wherein the leaching solvent is a sodium carbonate solution or a sodium dihydrogen phosphate solution; the pH value of the sodium molybdate leaching solution is 8-12, and the concentration of molybdenum in the sodium molybdate leaching solution is 50-200g/L.
S2, carrying out gas stripping deamination on the sodium molybdate leaching solution obtained in the step S1 to obtain a deaminated molybdenum-containing solution;
wherein the feed flow is 1-5m 3 H, vacuum degree of (40-80) kpa, steam flow of 0.1-0.7m 3 H; the content of ammonium radical in the deamination molybdenum-containing solution is less than 5mg/L.
S3, adding hydrogen peroxide into the deamination molybdenum-containing solution obtained in the step S2 for oxidation reaction to obtain an intermediate reaction solution;
wherein the concentration of the hydrogen peroxide is 30wt%, and the mass ratio of the hydrogen peroxide to the molybdenum in the deamination molybdenum-containing solution is 1: (1.5-6); the reaction time of the oxidation reaction is 0.5-2h.
S4, adding nitric acid into the intermediate reaction liquid obtained in the step S3 to adjust the pH value to be less than 0.5, heating for reaction at the temperature of 60-90 ℃ for 2-70h, and separating out molybdic acid crystals;
s5, filtering out the molybdic acid crystals obtained in the step S4, washing and drying to obtain high-purity molybdic acid;
washing molybdic acid crystals by using brine-free water, wherein the mass ratio of molybdic acid to brine-free water is 1: (1-2).
Example 1
S1, adding a leaching solvent into calcium molybdate serving as a raw material, wherein the leaching solvent is a sodium carbonate solution, the pH value of a sodium molybdate leaching solution is 10, and the concentration of molybdenum in the sodium molybdate leaching solution is 120g/L, so as to obtain a sodium molybdate leaching solution;
s2, carrying out gas stripping deamination on the sodium molybdate leaching solution obtained in the step S1, wherein the feeding flow is 3m 3 H, vacuum degree of-60 kpa, steam flow of 0.4m 3 H; the content of ammonium radicals in the deamination molybdenum-containing solution is less than 5mg/L, so as to obtain the deamination molybdenum-containing solution;
and S3, adding hydrogen peroxide into the deamination molybdenum-containing solution obtained in the step S2 for oxidation reaction, wherein the concentration of the hydrogen peroxide is 30wt%, and the mass ratio of the hydrogen peroxide to the molybdenum in the deamination molybdenum-containing solution is 1:4; the reaction time of the oxidation reaction is 1.7h, and an intermediate reaction solution is obtained;
s4, adding nitric acid into the intermediate reaction liquid obtained in the step S3 to adjust the pH value to be less than 0.5, heating for reaction at the temperature of 75 ℃ for 25 hours to separate out molybdic acid crystals;
and S5, filtering out the molybdic acid crystals obtained in the step S4, washing (washing the molybdic acid crystals by using brine-free water, wherein the mass ratio of molybdic acid to brine-free water is 1.
Example 2
S1, adding a leaching solvent into calcium molybdate serving as a raw material, wherein the leaching solvent is a sodium carbonate solution, the pH value of a sodium molybdate leaching solution is 8, and the concentration of molybdenum in the sodium molybdate leaching solution is 50g/L, so as to obtain a sodium molybdate leaching solution;
s2, carrying out gas stripping deamination on the sodium molybdate leaching solution obtained in the step S1, wherein the feeding flow is 1m 3 H, vacuum degree of-40 kpa, steam flow of 0.1m 3 H; the content of ammonium radicals in the deamination molybdenum-containing solution is less than 5mg/L, so as to obtain the deamination molybdenum-containing solution;
and S3, adding hydrogen peroxide into the deamination molybdenum-containing solution obtained in the step S2 for oxidation reaction, wherein the concentration of the hydrogen peroxide is 30wt%, and the mass ratio of the hydrogen peroxide to the molybdenum in the deamination molybdenum-containing solution is 1:6; the reaction time of the oxidation reaction is 0.5h, and an intermediate reaction solution is obtained;
s4, adding nitric acid into the intermediate reaction liquid obtained in the step S3 to adjust the pH value to be less than 0.5, heating for reaction at the temperature of 60 ℃ for 2 hours to separate out molybdic acid crystals;
and S5, filtering out the molybdic acid crystals obtained in the step S4, washing (washing the molybdic acid crystals by using brine-free water, wherein the mass ratio of molybdic acid to brine-free water is 1:1), and drying to obtain the high-purity molybdic acid A2.
Example 3
S1, adding a leaching solvent into calcium molybdate serving as a raw material, wherein the leaching solvent is a sodium carbonate solution, the pH value of a sodium molybdate leaching solution is 12, and the concentration of molybdenum in the sodium molybdate leaching solution is 200g/L, so as to obtain a sodium molybdate leaching solution;
s2, carrying out gas stripping deamination on the sodium molybdate leaching solution obtained in the step S1, wherein the feeding flow is 5m 3 H, vacuum degree of-80 kpa, steam flow of 0.7m 3 H; the content of ammonium radicals in the deamination molybdenum-containing solution is less than 5mg/L, so as to obtain the deamination molybdenum-containing solution;
and S3, adding hydrogen peroxide into the deamination molybdenum-containing solution obtained in the step S2 for oxidation reaction, wherein the concentration of the hydrogen peroxide is 30wt%, and the mass ratio of the hydrogen peroxide to the molybdenum in the deamination molybdenum-containing solution is 1:6; the reaction time of the oxidation reaction is 2 hours, and an intermediate reaction solution is obtained;
s4, adding nitric acid into the intermediate reaction liquid obtained in the step S3 to adjust the pH value to be less than 0.5, heating for reaction at 90 ℃ for 70h, and separating out molybdic acid crystals;
and S5, filtering out the molybdic acid crystals obtained in the step S4, washing (washing the molybdic acid crystals by using brine-free water, wherein the mass ratio of molybdic acid to brine-free water is 1:2), and drying to obtain the high-purity molybdic acid A3.
Examples of the experiments
The molybdic acid prepared in example 1 was subjected to electron microscope scanning.
As can be seen from the electron microscope scanning images (attached to FIGS. 1 and 2 in the specification), the molybdic acid particles are uniformly sized particles, and the single particles are in a loose chrysanthemum shape, which shows that the molybdic acid particles have good solubility.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for preparing high-purity molybdic acid from calcium molybdate is characterized by comprising the following steps:
s1, adding a leaching solvent into calcium molybdate serving as a raw material to obtain a sodium molybdate leaching solution;
s2, carrying out gas stripping deamination on the sodium molybdate leaching solution obtained in the step S1 to obtain a deaminated molybdenum-containing solution;
s3, adding hydrogen peroxide into the deamination molybdenum-containing solution obtained in the step S2 for oxidation reaction to obtain an intermediate reaction solution;
s4, adding nitric acid into the intermediate reaction liquid obtained in the step S3 to adjust the pH value, heating for reaction, and precipitating molybdic acid crystals;
s5, filtering out the molybdic acid crystals obtained in the step S4, washing and drying to obtain high-purity molybdic acid;
in step S2, the content of ammonium radicals in the deaminated molybdenum-containing solution is less than 5mg/L; in step S3, the mass ratio of the hydrogen peroxide to the molybdenum in the deaminated molybdenum-containing solution is 1: (1.5-6); in step S4, the pH value is less than 0.5, the heating temperature is 60-90 ℃, and the reaction time is 2-70h.
2. The method for preparing high-purity molybdic acid from calcium molybdate according to claim 1, wherein the leaching solvent is sodium carbonate solution or sodium dihydrogen phosphate solution in step S1.
3. The method according to claim 1, wherein in step S1, the pH of the sodium molybdate leach solution is 8 to 12, and the molybdenum concentration in the sodium molybdate leach solution is 50 to 200g/L.
4. The method of claim 1, wherein the feed rate during the gas stripping deamination step S2 is 1-5m 3 H, vacuum degree of (40-80) kpa, and steam flow of 0.1-0.7m 3 /h。
5. The method for preparing high-purity molybdic acid from calcium molybdate according to claim 1, wherein the concentration of hydrogen peroxide in step S3 is 30wt%.
6. The method for preparing high-purity molybdic acid from calcium molybdate according to claim 1, wherein the oxidation reaction is carried out for 0.5-2h in step S3.
7. The method of claim 1, wherein in step S5, the molybdic acid crystals are washed with brine-free water, and the mass ratio of molybdic acid to brine-free water is 1: (1-2).
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| CN1041145A (en) * | 1988-09-14 | 1990-04-11 | 云南省个旧市冶金研究所 | Sodium molybdate solution sinks the molybdenum pollution-free technology |
| CN103981379B (en) * | 2014-06-04 | 2015-08-12 | 北京矿冶研究总院 | Clean extraction method of wulfenite |
| CN104445411B (en) * | 2014-12-23 | 2016-04-20 | 金堆城钼业股份有限公司 | A kind of preparation method of macrobead molybdic acid |
| CN106698517B (en) * | 2016-12-28 | 2018-07-24 | 金堆城钼业股份有限公司 | A kind of preparation method of high-purity molybdic acid |
| CN108913916A (en) * | 2018-07-27 | 2018-11-30 | 成都虹波钼业有限责任公司 | A kind of method of molybdenum in normal pressure leaching calcium molybdate |
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Inventor after: Yang Wei Inventor after: Liu Jinrui Inventor after: Yi Jian Inventor after: Chen Wei Inventor after: Gao Zhiqiang Inventor after: Ren Qian Inventor before: Yang Wei Inventor before: Liu Jinyue Inventor before: Yi Jian Inventor before: Chen Wei Inventor before: Gao Zhiqiang Inventor before: Ren Qian |