CN1651341A - Depth purification method of multi metal ion solution in sulphate system - Google Patents

Abstract

A process for thoroughly cleaning the sulfate solution containing the ions of multiple metals includes such steps as adding (NH4)2SO4 to said solution, reacting to generate complex salt for removing the ions of multiple metals, separating, and using said complex salt to prepare soft-magnetic ferrite.

Description

Deep purification method of multi-metal ion solution in sulfate system

The invention relates to a method for deeply purifying a multi-metal ion solution or a single metal ion solution except zinc in a sulfate system.

[ background of the invention]High-purity high-quality raw materials and an advanced ferrite production process are required to prepare the high-performance soft magnetic ferrite. Such as the traditional ceramic method process, the purity of raw materials such as iron oxide red, manganese carbonate, zinc oxide and the like and main harmful impurity elements in the raw materials, such as k, Na, Si, Ca, Al₂O₃Etc. impose stringent requirements. The coprecipitation method utilizes coprecipitation reaction to simultaneously precipitate a plurality of metal ions in the solution to prepare ferrite powder, and the method has the advantages of more uniform mixing ratio of raw materials and mechanical mixing, easy control of granularity and granularity distribution, high powder activity, low sintering temperature and high product quality. But the coprecipitation method manufacturers all adopt pure metal or pure metal compounds as raw materials, and the cost is higher. ZL95110609.0 patent proposes that the mineral raw materials of the metal, or regenerated material are raw materials, remove heavy metal, fluoride precipitation removes calcium magnesium through leaching, sulfurizing precipitation at the same time, then coprecipitate and prepare manganese zinc ferrite coprecipitation powder, this process raw materials are cheap, the adaptive range is wide, the flow is short, therefore ferrite production cost is low;but harmful impurity elements in the coprecipitation powder are difficult to meet the requirements of the high-performance soft magnetic ferrite material.

[ summary of the invention]For the purpose of achieving Fe in sulfate systems²⁺、Mn²⁺、Zn²⁺The coprecipitation is carried out according to the proportion and is thoroughly separated from harmful impurity element ions, thereby realizing the deep purification.

The scheme adopted by the invention is as follows: at a temperature of 0-100 ℃ to [ M]²⁺]0 to 3.5mol/L (M represents Fe, Mn, Zn, etc.; however, [ M]is²⁺]At least one of the polymetal ion solutions of more than 0.5mol/l) is added with (NH)₄)₂SO₄100-700 g/L, adjusting the pH value to 0-6, cooling to 0-50 ℃, preserving heat for 10-420 min at the crystallization temperature, filtering to separate double salt and mother liquor, and washing with a small amount of 2-4 mol/L ammonium sulfate solutionAnd (3) salt, so as to obtain the multi-metal mixed double salt with a certain metal content ratio. The pure multi-metal double salt is a high-quality raw material for preparing soft magnetic coprecipitation powder. After the mother liquor is used for precipitating iron and manganese by using ammonium bicarbonate-ammonia or ammonium bicarbonate, the mother liquor returns to the leaching process, and when the system reaches the balance, the content proportion of each metal in the double salt can be ensured. Recovering (NH) from the solution after iron and manganese precipitation₄)₂SO₄。

The invention adopts M²⁺-SO₄ ^2--H₂O system (M represents metal such as Fe, Mn, Zn, etc.).

The method is suitable for simultaneous precipitation and deep impurity removal of double salts of a mixed solution of two or more metal ions, and is also suitable for precipitation and deep impurity removal of double salts of low-valence ions of single metals of manganese and iron.

The principle of the invention is as follows:

(1)

(2)

(3)

i.e. (NH)₄)₂SO₄With Fe²⁺、Mn²⁺、Zn²⁺The sulfate of the metal ions forms double salt deposition, so that the metal ions are thoroughly separated from harmful impurity element ions in the solution.

The invention has the advantages of thorough impurity removal and preservation of various main metals in proportion, and the mixed double salt product is a high-quality raw material for preparing high-quality soft magnetic coprecipitation powder. Is a key purification method for preparing the soft magnetic ferrite by a direct method.

[ description of the drawings]

FIG. 1: the principle process flow chart of the invention.

[ detailed description of the invention]

The present invention will be described in detail below with reference to the accompanying drawings.

Example 1

480mL of concentrated sulfuric acid is added into 3500mL of water, 178.6g of iron-manganese slag (containing Fe16.32% and Mn17.22%), 254g of scrap iron (containing Fe89.2%), 275g of pyrolusite (containing Mn36.91% and Fe8.86%) and 46g of zinc ash (containing Zn62.86%, Pb12.84% and Al) which are returned last time are respectively added₂O₃7.29 percent) and is simultaneously leached and purified according to the technological conditions of ZL95110606.0 patent invention, so as to obtain 4.03L of purified liquid, which comprises the following components (g/L): fe 62.97; mn 29.4; zn 5.87; 0.002% of Ca; mg 0.002; ni 0.035. (NH) is added to this cleaning solution₄)₂SO₄1998g, maintaining pH at 20 deg.C for 1.2, stirring for 1h, filtering to obtain pure mixed double salt 2230g, and dissolving with pure water 4000ml to obtain double solution 4360ml, which contains the following components (g/l): fe54.64, Mn18.08, Zn6.14, the bulk metal ratio (Fe: Mn: Zn ═ 69.29: 22.93: 7.78) is very close to the theoretical ratio (Fe: Mn: Zn ═ 69.05: 23.24: 7.71). The redissolution is prepared and coprecipitated according to the process conditions of ZL95110606.0 to prepare 557g coprecipitated powder, which comprises the following components in percentage by weight: fe 43.58, Mn 14.67, Zn 4.76, Ca 0.0086, Mg 0.013, Ni 0.028, Na 0.0020, Si 0.0016, Al 0.060, Cu 0.0098, Pb 0.0042, K0.0067, Cl 0.010, S0.047 and Cd0.00048, wherein the content of impurity elements is lower than that of the conventional coprecipitation method, and the actual ratio of main metals (Fe: Mn: Zn: 69.16: 23.28: 7.55) is closer to the theoretical ratio.

Example 2

348.63g of manganese carbonate ore powder (containing Mn21.16% and Fe2.61%) is used to replace pyrolusite, 4180ml of purified liquid is prepared according to the method and conditions of the embodiment 1, and the components (g/l) are as follows: fe 59.95, Mn 17.49, Zn13.65, Ca 0.005 and Mg 0.002. (NH) is added to this cleaning solution₄)₂SO₄2215g, stirring at 25 deg.C and pH 1.5 for 1.5h, filtering to obtain 2202g of pure mixed double salt, and processing as in example 1And carrying out re-dissolution liquid preparation and coprecipitation under the conditions to obtain 540g of coprecipitation powder, wherein the components in percentage by weight are as follows: fe 40.91, Mn 9.82, Zn 10.48, Ca 0.0027, Mg 0.0010, Ni0.0017, Na 0.0054, Si 0.0017, Al 0.061, Cu 0.00057, Pb 0.0062, K0.0068, Cl 0.0095, S0.032 and Cd 0.0019, which shows that the actual ratio of main metals (Fe: Mn: Zn ═ 66.853: 16.043: 17.12(wt)) is still very close to the theoretical ratio (Fe: Mn: Zn ═ 66.87: 15.81: 17.32) in the case of raw material replacement, and the content of impurity elements is lower than that of the conventional coprecipitation method.

Example 3

70.4L of water is firstly added into a 100L electric heating enamel kettle, 9.6L of concentrated sulfuric acid is added into the electric heating enamel kettle in a diffused way, 3.377kg of iron-manganese slag (containing Fe17.46 percent and Mn18.21 percent) returned last time is respectively added into the electric heating enamel kettle, 8.0kg of pyrolusite, 6.29kg of scrap iron and 0.92kg of zinc ash which have the same components as those in the embodiment 1 are simultaneously leached according to the process conditions of ZL95110606.0, and are simultaneously purified, 73L of purified liquid is obtained, and the components (g/L) are as follows: fe75.34, Mn 29.23, Zn 7.55, Ca 0.001 and Mg 0.0027. (NH) is added to this cleaning solution₄)₂SO₄62.256kg, stirring at 35 deg.C pH 3.0 for 75min, filtering to obtain pure mixed double salt 45.8kg, and performing redissolution and coprecipitation according to the method and conditions of example 1 to obtain 11.427kg of coprecipitated powder, which comprises the following components (by weight%): fe 41.71, Mn 14.23, Zn 4.39, Ca 0.012, Mg 0.0045, Ni0.038, Na 0.0015, Si0.0014, Al 0.040, Cu 0.00028, Pb 0.0053, K0.0035, Cl 0.0095, S0.11 and Cd 0.0015, which shows that under the condition of 20 times of scale amplification, the actual ratio of the main metals (Fe: Mn: Zn ═ 69.13: 23.59: 7.28) is still very close to the theoretical ratio (Fe: Mn: Zn ═ 69.05: 23.24: 7.71), and particularly, the content of impurity elements is still lower than that of the conventional coprecipitation method.

Claims (4)

1. The deep purification method of the multi-metal ion solution in the sulfate system is characterized in that: at a temperature of 0-100 ℃ to [ M]²⁺]Adding (NH) into 0-3.5 mol/L multi-metal ion solution₄)₂SO₄100-700 g/L, adjusting the pH value to 0-6, cooling to the temperature of 0-50 ℃, preserving the heat for 10-420 min at the crystallization temperature, filtering and separating the double salt and the mother liquor, and then using a small amount of 2-4 moAnd washing the double salt with an l/l ammonium sulfate solution to obtain the multi-metal mixed double salt with a certain metal content ratio.

2. The method of claim 1, wherein: the solution of said multi-metal ions is Fe²⁺、Mn²⁺、Zn²⁺Mixed solution of two or more metal ions with similar properties or single metal ion solution except zinc.

3. The method of claim 1, wherein: the obtained double salt product is a multi-metal mixed double salt or a manganese-iron single metal double salt with a certain proportion, and the double salts are further used for preparing the soft magnetic ferrite.

4. The method of claim 1, wherein: the double-salt mother liquor is leached back by using ammonium carbonate-ammonia or iron-manganese slag precipitated by ammonium carbonate to ensure that the proportion of metal ions is not changed.