CN1039637C

CN1039637C - Method for producing high-purity manganese carbonate by using pyrolusite

Info

Publication number: CN1039637C
Application number: CN94113105A
Authority: CN
Inventors: 杨健; 李宗雄; 贺万宁
Original assignee: Changsha Research Institute Of Mining And Metallurgy ministry Of Metallurgical Industry
Current assignee: Changsha Research Institute Of Mining And Metallurgy ministry Of Metallurgical Industry
Priority date: 1994-10-18
Filing date: 1994-10-18
Publication date: 1998-09-02
Anticipated expiration: 2014-10-18
Also published as: CN1121049A

Abstract

The invention relates to a method for producing high-purity manganese carbonate by using pyrolusite. The method is characterized in that: removing calcium and magnesium impurities in pyrolusite by taking the pyrolusite as a raw material; reducing and leaching by using a proper reducing agent, removing potassium and sodium ions in the solution while leaching, and adding sulfide to purify and remove heavy metal ions in the leaching solution to obtain a qualified manganese sulfate solution; mixing the manganese sulfate solution and the carbonate solution, and preparing a precipitate product under optimized process conditions; washing and drying the product to obtain the high-purity manganese carbonate, which comprises the following main chemical components (%): mn 44-46, SO^2- ₄≤0.05、Ca≤0.03、Mg≤0.02、K≤0.01、Na≤0.01。

Description

Method with production of high-purity manganese carbonate with pyrolusite

The invention relates to the pyrolusite is the method that raw material is produced high-purity manganese carbonate.

The domestic production high-purity manganese carbonate is a raw material with manganese metal or synthetic Manganse Dioxide generally at present, and dissolving makes manganese nitrate solution in the salpeter solution system, produces as precipitation agent with the soluble carbon hydrochlorate then.Its shortcoming is synthetic Manganse Dioxide of feed metal manganese and nitric acid expensive price, the production cost height.In order to reduce production costs, be raw material with the ore, leaching in the sulphuric acid soln system is a valid approach.As day the disclosure specially permit flat 4-108614 and propose, be raw material with the pyrolusite, through reducing roasting, the sulphuric acid soln system leaches, and the soluble carbon hydrochlorate is made precipitation agent, makes manganous carbonate, its chemical ingredients (%): Mn 44.0～44.2.Ca 0.042～0.140, Mg 0.011～0.044, SO ₄ ^2-0.59～1.51, Na 0.036～0.086, K 0.011～0.019.And for example Deutsches Reichs-Patent DE3408030A1 proposes, and is raw material with the pyrolusite, and through reducing roasting, the sulphuric acid soln system leaches, and sal volatile is made precipitation agent, makes manganous carbonate, and foreign matter content is (%): SO ₄ ^2-0.7, Ca0.26, NH ₄ ⁺0.10.These patents all attempt to set up the method for low cost production highland manganous carbonate, but impurity SO in the product ₄ ^2-, Ca, Mg, K, Na content is higher, can not satisfy the requirement of the required manganous carbonate of soft magnetic ferrite.

The objective of the invention is to set up a kind of is raw material with the pyrolusite, produces the method for high-purity manganese carbonate.It focuses on controlling impurity SO in the product ₄ ^2-, Ca, Mg, K, Na content.

For achieving the above object, the main technical schemes of Ben Jiaoming is: in sulphuric acid soln pyrolusite is carried out preextraction and washup operation and remove Ca, Mg impurity, select for use Ca, reductive agent that the Mg foreign matter content is low to reduce leaching, the qualified manganese sulfate solution that obtains slowly mixes with carbonate solution, throw out makes high-purity manganese carbonate through washing, oven dry.Fig. 1 is seen in technical process of the present invention.The chemical ingredients of its raw material pyrolusite is (%): TMn 30～50, CaO 0.2～5.0, MgO 0.2～5.0, Al ₂O ₃3～5, SiO ₂5～20, K ₂O 0.5～3.0, Na ₂O 0.5～3.0.

Technological process division of the present invention is as follows:

One, breeze is at acidity H ₂SO ₄5～100g/l, solid-to-liquid ratio 1: 2～10,20～100 ℃ of temperature, preextraction under time 0.5～5h condition, impurity such as calcium, magnesium enter solution, and the manganese leaching yield is less than 1%.Then, at normal temperatures, with solid-to-liquid ratio 1: 2～10, the decantation solid-liquid separation is with deionized water washup 1～5 time.

Two, the pyrolusite ore pulp after washing imports leaching vat, selects for use to contain CaO less than 0.3%, and MgO reduces leaching less than 0.2% sulfide reductive agent.Its processing condition are: solid-to-liquid ratio 1: 2～10, and pyrolusite, reductive agent weight ratio 1: 0.5～2.0, sour ore deposit is than 3～0.5: 1,40～100 ℃ of temperature, time 1～10h.In the process that leaches, utilize that self component reacts to each other in the system, make potassium, sodium ion form title complex precipitation and solution separating.Add the ammoniacal liquor neutralization, leach ore pulp terminal point pH greater than 5.0.After solid-liquid separation, exceed standard as beavy metal impurity ion content in the supernatant liquor, then add sulfide (wherein CaO content is less than 0.3%, and MgO is less than 0.2%) removal of impurities.The manganese sulfate solution composition that makes is (g/l): Mn ²⁺40～100, Ca 0.01～0.05, and Mg 0.01～0.05, and K 0.03～0.1, and Na 0.02～0.1.

Three, the manganese sulfate solution and the carbonate solution of preparation is slowly mixed, control pH5～9,10～80 ℃ of temperature.The precipitated product that obtains deionized water wash 3～7 times, its solid-to-liquid ratio is 1: 3～10.Filter at last, dry, 50～100 ℃ of bake out temperatures.The high-purity manganese carbonate that makes can satisfy the requirement of the used manganous carbonate of soft magnetic ferrite, and its chemical ingredients is (%): Mn Cl ^-SO ₄ ^2-SiO ₂Al K Na Ca Mg Pb44-46≤0.01≤0.05≤0.01≤0.01≤0.01≤0.01≤0.03≤0.02≤0.01

Embodiment one:

Certain pyrolusite 70g, chemical ingredients (%): T _Mn47.13, CaO 0.23, MgO 0.82, Al ₂O ₃4.52, SiO ₂5.25, K ₂O 1.32, Na ₂O 0.60.Add sulfuric acid 6.0g, 80 ℃ of temperature, time 2.Oh, carry out preextraction; Its underflow is with solid-to-liquid ratio washup at normal temperatures in 1: 63 times.Pretreated pyrolusite under 90 ℃ of solid-to-liquid ratios 1: 3, temperature, is added sulfuric acid 150g, Na ₂S (wherein CaO content is less than O.3%, and MgO is less than 0.2%) 80g, leach through reduction in 7 hours, leach liquor 463ml, contain Mn ²⁺58.8g/l, manganese yield 82.5%.

With above-mentioned manganese sulfate solution 300ml, under normal temperature, slowly join 338ml and contain NH ₄HCO ₃In the solution of 150g/l, the throw out that obtains makes high-purity manganese carbonate through washing, oven dry, and chemical ingredients is (%): Mn 45.45, SO ₄ ^2-0.040, Ca 0.023, Mg＜0.01, K≤0.01, Na≤0.02.

Embodiment two:

Above-mentioned pyrolusite 420g adds sulfuric acid 45.0g, 95 ℃ of temperature, time 2.0h, carries out preextraction.The preextraction underflow is with solid-to-liquid ratio 1: 5, washup at normal temperatures 2 times.Pretreated pyrolusite under 95 ℃ of solid-to-liquid ratios 1: 3, temperature, is added sulfuric acid 960g, grey black (wherein CaO content is less than 0.3%, and MgO is less than 0.2%) 480g, leaches through reduction in 8 hours, leach liquor 2.64l, contain Mn ²⁺57.3g/l, manganese yield 76.4%.

Get the manganese sulfate solution 300ml of preparation, slowly join 329ml at normal temperatures and contain NH ₄HCO ₃In the solution of 150g/l, the throw out that obtains makes high-purity manganese carbonate, chemical ingredients (%): Mn 44.69, SO through washing, oven dry ₄ ^2-0.037, K≤0.01, Na≤0.02, Ca≤O.03, Mg≤0.02, Cl ^-≤ 0.01, SiO ₂≤ 0.01, Al≤0.01, Pb≤O.01.

Advantage of the present invention is: the present invention is take pyrolusite as raw material, in the sulfuric acid solution system, leach, thus high purity carbonic acid Manganese. The used prices of raw and semifnished materials are cheap, can the decrease production cost; Products obtained therefrom is superior in quality, can satisfy soft magnet The oxysome requirement of manganese carbonate.

Claims

1. one kind is the method that raw material is produced high-purity manganese carbonate with pyrolusite, it is characterized in that: be raw material with the pyrolusite, carry out sulfuric acid pre-treatment and washup operation and remove calcium, magnesium addition in the pyrolusite; Then with solid-to-liquid ratio 1: 2～10, pyrolusite, reductive agent weight ratio 1: 0.5～2.0, sour ore deposit is than 3～0.5: 1,40～100 ℃ of temperature, time 1～10h reduces leaching, and removes potassium, sodium ion in the solution with the form of title complex simultaneously; Ore pulp is through solid-liquid separation, removes heavy metal ion in the solution with sulfide, obtains qualified manganese sulfate solution; This manganese sulfate solution and carbonate solution is mixed, by optimizing processing condition, manganese and sulphate content in the control precipitated product; Precipitated product makes high-purity manganese carbonate through washing, oven dry.

2. the method for production high-purity manganese carbonate according to claim 1, the condition when it is characterized in that preextraction is: solid-to-liquid ratio 1: 2～10,20～100 ℃ of temperature, time 0.5～5h, ore pulp contains H ₂SO ₄5～100g/l; The condition of washup operation is: solid-to-liquid ratio 1: 2～10, decant separates, washup 1～5 time.

3. the method for production high-purity manganese carbonate according to claim 1 is characterized in that selecting for use when reduction is leached containing CaO less than 0.3%, and MgO is less than 0.2% sulfide reductive agent.

4. the method for production high-purity manganese carbonate according to claim 1 is characterized in that the processing condition that precipitate manganous carbonate are: control PH5～9,10～80 ℃ of temperature.