CN101704555A

CN101704555A - Method for circularly purifying manganese sulfate and manganese carbonate

Info

Publication number: CN101704555A
Application number: CN200910161306A
Authority: CN
Inventors: 姜志光; 华东
Original assignee: Shenzhen Haoyitong Investment & Development Co Ltd; BEIJING WANKUN JIAHONG SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
Current assignee: Shenzhen Haoyitong Investment & Development Co Ltd; BEIJING WANKUN JIAHONG SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd; Guizhou Redstar Developing Co Ltd
Priority date: 2009-07-20
Filing date: 2009-07-20
Publication date: 2010-05-12
Also published as: WO2011009351A1

Abstract

The invention relates to a method for circularly purifying manganese sulfate and manganese carbonate. The method comprises the following steps: A, stirring manganese sulfate solution at the temperature of between 40 and 80 DEG C, and adding ammonium bicarbonate into the solution for synthesis, controlling the synthesis end point to be an equimolar reaction, separating solid, and washing the solid with hot water to prepare manganese carbonate; B, adding the prepared manganese carbonate into 6 to 12mol/L H2SO4 for reaction, controlling the pH value of the reaction solution to be between 1 and 2, and heating and boiling the solution; C, adding the manganese carbonate prepared in the step A into the reaction solution in the step B, and adjusting the pH value of the solution back to be 4 to 5; and D, performing solid-liquid separation on the reaction solution, distilling and crystallizing the prepared filtrate, and drying the crystal to prepare the manganese sulfate. The circularly purifying method can prepare high-purity manganese sulfate and manganese carbonate with low calcium magnesium and low potassium and sodium.

Description

The method for circularly purifying of a kind of manganous sulfate and manganous carbonate

Technical field

The present invention relates to the purifying technique of manganous sulfate and manganous carbonate, particularly the circulation purifying technique of manganous sulfate and manganous carbonate.

Background technology

Along with the development of lithium manganate secondary cell, its requirement to manganous sulfate and manganous carbonate material also exceedes height.Except size-grade distribution, heavy metal content have higher requirements, also there are higher requirement, particularly power cell strict more in this to the requirement of this type of material to basic metal in the material and alkaline-earth metal.The content of alkaline-earth metal and basic metal, particularly calcium ions and magnesium ions can not satisfy the development need of current lithium manganate secondary cell in manganous carbonate that prior art provides and the manganous sulfate material.

For the preparation of manganous sulfate, inventor place company utilizes Manganse Dioxide breeze and SrS or BaS reaction to obtain manganese monoxide, after washing with manganese monoxide and H ₂SO ₄300～450g/L manganese sulfate solution of prepared in reaction low-heavy metal content, with this solution through acidifying and add H ₂O ₂Post-heating is handled removing sulfide, and obtains the manganous sulfate settled solution after filtration.

Certainly the present invention also can utilize commercially available manganous sulfate as the raw material purification that circulates.

Summary of the invention

The present invention utilizes the impurity separating power in manganous sulfate and the manganous carbonate building-up process, and circulation separates high-quality manganous sulfate of preparation and manganous carbonate material.Basic metal is not participated in reaction in this synthetic system, it is stayed in the mother liquor when carbonate synthesis manganese solid-liquid separation, thereby reaches the separation purpose.The supercarbonate solubleness of calcium is very big simultaneously, has also stayed in the mother liquor, and the carbonate of magnesium under the ammonia condition does not precipitate, thereby reaches the separation purpose.So the present invention is from manganous sulfate carbonate synthesis manganese, and then K, Na, Ca, Mg have just obtained effective separation during the preparation manganous sulfate.The chemical equation that the present invention relates generally to has:

MnSO ₄+2NH ₄HCO ₃→MnCO ₃+(NH ₄) ₂SO ₄+CO ₂↑

MnCO ₃+H ₂SO ₄+H ₂O→MnSO ₄·H ₂O+CO ₂↑

The present invention can obtain in the used manganous sulfate market, and the dissolving manganous sulfate just has been mixed with manganese sulfate solution in water.

With manganese sulfate solution and NH ₄HCO ₃It is synthetic that solution or solid carry out carbonating, and moles such as control compound agent obtain manganous carbonate removes deentrainment through washing (NH with separating calcium and magnesium impurity ₄) ₂SO ₄, and make it and 12mol/LH ₂SO ₄React, after filtration, evaporative crystallization obtains high-quality manganous sulfate material, also can carry out the high-quality manganous carbonate material of the synthetic acquisition of carbonating simultaneously once more.For further understanding technological process of the present invention, Fig. 1 represents the synthesis route figure of manganous carbonate and manganous sulfate with simple diagram.

Manganous sulfate of the present invention and manganous carbonate method for circularly purifying are specific as follows:

Manganese sulfate solution at 40-80 ℃, is preferably the 50-60 ℃ of slow bicarbonate of ammonia that adds of mole such as stirring down, and separate solid is made manganous carbonate with 80-100 ℃ hot wash, and hot wash can be washed by 1: 5 material-water ratio; Above-mentioned manganous carbonate is added 6-12mol/L, be preferably 6-9mol/L H ₂SO ₄Reaction, control reaction soln pH value is 1-2, heated and boiled, it mainly is fully to react for manganous carbonate and sulfuric acid that pH value is transferred in this place; Be 4-5 with in the above-mentioned manganous carbonate adding reaction soln that makes the solution pH value being adjusted back then; With the reaction soln solid-liquid separation, gained filtrate (manganese sulfate solution) evaporative crystallization, oven dry obtains manganous sulfate then, also gained filtrate can be repeated the first step as manganese sulfate solution and prepare high-purity manganese carbonate. and the control for mole adding bicarbonate of ammonia such as B in above each step relate to can utilize chemical determination [Mn ²⁺] and [CO ₃ ^2-] concentration control reaction end.

Description of drawings

Fig. 1 is a main technique schema of the present invention.

Embodiment

Embodiment 1

With 354g/L MnSO ₄Solution 4000ml places the 5000ml beaker, and 50 ℃ of controlled temperature stir down slowly adding food grade NH ₄HCO ₃1514g, suction strainer separates, and filtrate is reclaimed (NH ₄) ₂SO ₄, solid is washed secondary by 80 ℃ of heat of 1: 5 material-water ratio, gets partially desiccated and becomes MnCO ₃1 ^#

Manganous carbonate after the above-mentioned washing is placed the 5000ml beaker, add the small amount of deionized water making beating, use 6mol/L H ₂SO ₄React to pH value be 1, after the heated and boiled with the washing after MnCO ₃The readjustment pH value is 4, and with qualitative filter paper filtration at a slow speed, filter residue is abandoned, and filtrate evaporative crystallization, exsiccation are placed in 80～85 ℃ of baking ovens and dried 20 hours, obtain MnSO ₄H ₂O sample 1 ^#

Embodiment 2

With 354g/L MnSO ₄Solution places the 5000ml beaker, and 55 ℃ of controlled temperature stir down slowly adding food grade NH ₄HCO ₃1514g, suction strainer separates, and filtrate is reclaimed (NH ₄) ₂SO ₄, solid is washed secondary by 100 ℃ of heat of 1: 5 material-water ratio.

With MnCO after the above-mentioned washing ₃Add the small amount of deionized water making beating, use 9mol/L H ₂SO ₄React to pH value be 2, after the heated and boiled with the washing after MnCO ₃Pulling back to pH value is 5, and with qualitative filter paper filtration at a slow speed, filter residue is abandoned, and filtrate places the 5000ml beaker, and 55 ℃ of scopes of controlled temperature slowly add and wait mole NH ₄HCO ₃Synthetic, solid-liquid separation, liquid phase reclaims (NH ₄) ₂SO ₄, solid is washed secondary by 100 ℃ of heat of 1: 5 material-water ratio, and dehydration is placed in 85 ℃ of vacuum drying ovens and dried 16 hours, obtains MnCO ₃Sample 2 ^#

Embodiment 3

Repeat embodiment 1, that different is the 12mol/L H that adds ₂SO ₄, be 60 ℃ in temperature and stir slowly adding food grade NH in manganous sulfate liquid down ₄HCO ₃, get MnCO ₃Sample 3 ^#And MnSO ₄H ₂O sample 3 ^#

Embodiment 4

Repeat embodiment 2, different is under 80 ℃, stirs slowly to add food grade NH ₄HCO ₃, obtain MnCO ₃Sample 4 ^#

More than each embodiment gained sample MnCO ₃Content and foreign matter content data such as following table:

Content	??1 ^#	??1 ^#	??2 ^#	??3 ^#	??3 ^#	??4 ^#
Content	??1 ^#	??1 ^#	??2 ^#	??3 ^#	??3 ^#	??4 ^#	??MnCO ₃(weight %)	??99.54		??99.71	??99.56		??99.68

Content	??1 ^#	??1 ^#	??2 ^#	??3 ^#	??3 ^#	??4 ^#
Content	??1 ^#	??1 ^#	??2 ^#	??3 ^#	??3 ^#	??4 ^#	??MnSO ₄·H ₂O (weight %)		??99.62			??99.70
??Ca	??231ppm	??33ppm	??19ppm	??223ppm	??34ppm	??24ppm	??MnSO ₄·H ₂O (weight %)		??99.62			??99.70
??Ca	??231ppm	??33ppm	??19ppm	??223ppm	??34ppm	??24ppm	??Mg	??16ppm	??3.1ppm	??1.4ppm	??17ppm	??3.4ppm	??1.6ppm
??K	??9.2ppm	??2.0ppm	??＜1ppm	??10ppm	??2.3ppm	??＜1ppm	??Mg	??16ppm	??3.1ppm	??1.4ppm	??17ppm	??3.4ppm	??1.6ppm
??K	??9.2ppm	??2.0ppm	??＜1ppm	??10ppm	??2.3ppm	??＜1ppm	??Na	??6.5ppm	??0.4ppm	??＜1ppm	??6.8ppm	??0.5ppm	??＜1ppm

Claims

1. manganous sulfate and manganous carbonate method for circularly purifying, it comprises step:

A stirs adding bicarbonate of ammonia with manganese sulfate solution and synthesizes under 40-80 ℃ of temperature range, the control synthetic end point is a reaction with same mole, separate solid, and manganous carbonate is made in hot wash;

B adds 6-12mol/L H with the above-mentioned manganous carbonate of making ₂SO ₄Reaction, control reaction soln pH value is 1-2, heated and boiled;

The manganous carbonate that C makes with steps A adds in the reaction soln of step B, and solution pH value readjustment is 4-5;

D is step C gained reaction soln solid-liquid separation, gained filtrate evaporative crystallization, dry then manganous sulfate.

2. manganous sulfate as claimed in claim 1 and manganous carbonate method for circularly purifying prepare manganous carbonate with step D gained filtrate as manganese sulfate solution repeating step 1.

3. manganous sulfate as claimed in claim 1 or 2 and manganous carbonate method for circularly purifying, wherein the temperature range described in the A step is 50-60 ℃.

4. manganous sulfate as claimed in claim 1 or 2 and manganous carbonate method for circularly purifying wherein add H in the B step ₂SO ₄Volumetric molar concentration be 6-9mol/L.

5. manganous sulfate as claimed in claim 1 or 2 and manganous carbonate method for circularly purifying wherein, utilize chemical determination [Mn in the B step ²⁺] and [CO ₃ ^2-] concentration control reaction end.

6. manganous sulfate as claimed in claim 1 or 2 and manganous carbonate method for circularly purifying, wherein, the temperature of described hot wash is 80-100 ℃.

7. manganous sulfate as claimed in claim 1 or 2 and manganous carbonate method for circularly purifying, wherein, the solid of gained was by material-water ratio washing in 1: 5 in the steps A.