CN102701292A

CN102701292A - Preparation method of cobalt carbonate material with compact structure and spheroid shape

Info

Publication number: CN102701292A
Application number: CN2012101730638A
Authority: CN
Inventors: 吉鸿安; 朱来东; 王同敏
Original assignee: Northwest Research Institute of Mining and Metallurgy
Current assignee: Northwest Research Institute of Mining and Metallurgy
Priority date: 2012-05-30
Filing date: 2012-05-30
Publication date: 2012-10-03
Anticipated expiration: 2032-05-30
Also published as: CN102701292B

Abstract

The invention discloses a preparation method of a cobalt carbonate material with a compact structure and a spheroid shape, and aims to solve the problems of loose microstructure, disordered shape and poor uniformity of the cobalt carbonate material prepared by a conventional method. The preparation method comprises the following specific steps: placing a cobalt chloride solution with system temperature, pH value and cobalt concentration meeting the requirements into a reaction kettle, and keeping the cobalt chloride solution relatively constant; uniformly adding an ammonium bicarbonate solution into a cobalt solution system according to a certain flow, and taking a limited pH value as a reaction end point parameter of a control system; aging for a certain time, filtering, and repeatedly washing to obtain the required cobalt carbonate material. The cobalt carbonate material prepared by the method has the characteristics of spheroidal morphology, uniform particle size, compact structure and better particle size distribution, adopts standard conventional equipment, is easy to control process parameters, is simple to operate and is suitable for large-scale production.

Description

A kind of compact structure, globoid pattern cobaltous carbonate preparation methods

Technical field

The invention belongs to new forms of energy, field of new; Relate to the cobaltous carbonate preparation methods that microscopic appearance and physicals is had characteristic requirements, the cobaltous carbonate that this preparation method makes can be used for producing the precursor raw material of the powder blue product of battery material, wimet, electronic material etc.

Background technology

Flourish along with electronics, communications industry, various household electrical appliance, mobile phone, notebook computer are doubled and redoubled to the demand of lithium-ion secondary cell, and tricobalt tetroxide has also obtained quick progress as its production technology of important source material of lithium cell cobalt acid lithium material.Powder blue (particularly tricobalt tetroxide) product appearance is grey black or black powder; Be a kind of important transition metal oxide, usually as main raw material and the tinting material of ceramic industry and the catalyzer in the chemical industry of producing wimet, battery material, electronic material.In chemical industry, Co ₃O ₄It is a kind of efficient, persistent catalyzer.The working method of the used cobaltous carbonate precursor of powder blue is more at present; Routine joins carbonate solution and cobalt salt solution in the reaction vessel; The cobaltous carbonate that makes is invisible in a jumble because of its throw out particle aggregation bodily form looks, loose frangible powder blue that only can the production common grade when producing powder blue with precursor material, more is difficult to satisfy the needs that battery material etc. is produced required " globoid pattern densification high-quality carbonic acid cobalt precursor material ".

Summary of the invention

The purpose of this invention is to provide a kind of compact structure, globoid pattern cobaltous carbonate preparation methods, loose with the cobaltous carbonate material microstructure that solves the preparation of conventional working method, pattern mixed and disorderly, the problem of lack of homogeneity.

Technical scheme of the present invention is following:

A kind of compact structure, globoid pattern cobaltous carbonate preparation methods is characterized in that concrete steps are following:

Figure 2012101730638100002DEST_PATH_IMAGE001

will be through filtering, and cobalt concentration is that the cobalt chloride solution of 1～2 mol/L, pH value 4.75～5.20 is inserted in the reaction kettle;

is under agitation condition; Heating steps

solution; Make the solution system temperature be controlled at 55～65 ℃, and keep system temperature relatively stable;

Figure 2012101730638100002DEST_PATH_IMAGE003

the pre-filtered and the concentration of 1.8 ~ 2.5? mol / L ammonium bicarbonate solution was 250 ~ 800L / h flow rate of uniform spray to step

of the system;

Solution system pH value 7.0～7.5 promptly stops the interpolation of ammonium bicarbonate soln as the system reaction end in

controlled step

;

is with 20～40 minutes after-filtration of step

gained solid-liquid system ageing; Repetitive scrubbing promptly gets material requested.

The present invention adopts the conversion unit of standard normal just can produce " compact structure, globoid pattern cobaltous carbonate material ".This method as reaction system, is utilized the spontaneous adsorbent solution medium ionic effect in solution of throw out particle, the IT of adjustment system based on cobalt chloride solution the most common, the marketization; Simultaneously, in the chemical precipitation process, nascent particulate is easy to the selective adsorption ion identical with its composition from solution; Make the throw out particle surface charged, produce double electrical layers, help improving dispersion of particles property at solid-liquid interface; Be reduced to nuclear energy and build, form the particle aggregation electricity and build, help dispersion of particles; Prevented particle aggregation to a certain extent, also comprised dispersion process and agglomeration in the sedimentary in addition process of growth, when two phase mixing systems reach balance; System can change to making the total surface free energy be tending towards minimum direction; The result has the small-particle dissolving of high surfaces free energy and macrobead is able to growth, makes particle size distribution trend homogeneous, thus the pattern of control particle.Agglomeration accounts for consequence in the process of growth of particle.In the cobalt salt system, reunion is the main mode of particle growth.In the particle growth process, growth velocity reduces with the increase of particle radius, finally also can form the consistent particle aggregate of epigranular.After small-particle gathers on the macroparticle, can " fusing " among macroparticle, form a bigger integral particles through surface reaction, surface diffusion or volume diffusion; But also possibly only between particle, be in contact with one another place's local " fusing ", form a porous granule.If " fusing " reaction is enough fast; Promptly " fuse " pitch time of required time of reaction less than the adjacent secondary effective collision of particle; Then can form a bigger integral particles cluster of grains, otherwise then form the porous granule aggregate through assembling, thus the control particle size.

The advantage that the cobaltous carbonate material of the inventive method preparation has is:

cobaltous carbonate material microscopic appearance be globoid, particle size evenly, compact structure and the preferable characteristic of size-grade distribution.

adopts standard normal equipment; Processing parameter is easy to control; Simple to operate, be fit to large-scale production.

Description of drawings

Fig. 1 is the globoid pattern structure iron that the embodiment of the invention 1 makes material;

Fig. 2 is the particle size distribution figure that the embodiment of the invention 1 makes material;

Fig. 3 is the globoid pattern structure iron that the embodiment of the invention 2 makes material;

Fig. 4 is the particle size distribution figure that the embodiment of the invention 2 makes material;

Fig. 5 is the globoid pattern structure iron that the embodiment of the invention 3 makes material;

Fig. 6 is the particle size distribution figure that the embodiment of the invention 3 makes material;

Fig. 7 is the globoid pattern structure iron that the embodiment of the invention 4 makes material;

Fig. 8 is the particle size distribution figure that the embodiment of the invention 4 makes material.

Embodiment

Following embodiment can further specify structure and the physical index characteristic that present method prepares the cobaltous carbonate material, and institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.

Embodiment 1

will be through filtering, and the cobalt chloride solution of cobalt concentration 1.0 mol/L, pH value 4.75 is inserted in the reaction kettle;

is under agitation condition; Heating steps

solution; Make the solution system temperature be controlled at 55 ℃, and keep system temperature relatively stable;

will be pre-filtered and the concentration of 1.8? mol / L of ammonium bicarbonate solution to 800L / h flow uniform spray to step

of the system;

Solution system pH value 7.5 promptly stops the interpolation of ammonium bicarbonate soln as the system reaction end in

controlled step

;

is with 20 minutes after-filtration of step

Embodiment 1 makes globoid pattern structure and size-grade distribution such as Fig. 1 and Fig. 2 of material, and physical index " granularity and density measurement result " is like table 1.

Embodiment 2

will be through filtering, and the cobalt chloride solution of cobalt concentration 1.5 mol/L, pH value 4.80 is inserted in the reaction kettle;

is under agitation condition; Heating steps solution; Make the solution system temperature be controlled at 63 ℃, and keep system temperature relatively stable;

will be pre-filtered and the concentration of 2.0? mol / L of ammonium bicarbonate solution to 588L / h flow uniform spray to step

of the system;

Solution system pH value 7.2 promptly stops the interpolation of ammonium bicarbonate soln as the system reaction end in

controlled step ;

is with 30 minutes after-filtration of step

Embodiment 2 makes globoid pattern structure and size-grade distribution such as Fig. 3 and Fig. 4 of material, and physical index " granularity and density measurement result " is like table 1.

Embodiment 3

will be through filtering, and the cobalt chloride solution of cobalt concentration 1.6 mol/L, pH value 5.09 is inserted in the reaction kettle;

is under agitation condition; Heating steps

solution; Make the solution system temperature be controlled at 60 ℃, and keep system temperature relatively stable;

will be pre-filtration and concentration of 1.86? mol / L of ammonium bicarbonate solution to 280L / h flow uniform spray to step

of the system;

controlled step

;

is with 30 minutes after-filtration of step gained solid-liquid system ageing; Repetitive scrubbing promptly gets material requested.

Embodiment 3 makes globoid pattern structure and size-grade distribution such as Fig. 5 and Fig. 6 of material, and physical index " granularity and density measurement result " is like table 1.

Embodiment 4

will be through filtering, and the cobalt chloride solution of cobalt concentration 2.0 mol/L, pH value 5.20 is inserted in the reaction kettle;

is under agitation condition; Heating steps

solution; Make the solution system temperature be controlled at 65 ℃, and keep system temperature relatively stable;

will be pre-filtered and the concentration of 2.5? mol / L of ammonium bicarbonate solution to 250L / h flow uniform spray to step

of the system;

Solution system pH value 7.0 promptly stops the interpolation of ammonium bicarbonate soln as the system reaction end in

controlled step

;

is with 40 minutes after-filtration of step

Embodiment 4 makes globoid pattern structure and size-grade distribution such as Fig. 7 and Fig. 8 of material, and physical index " granularity and density measurement result " is like table 1.

Cobaltous carbonate granularity that table 1 embodiment makes and density measurement result

Claims

1. a compact structure, globoid pattern cobaltous carbonate preparation methods is characterized in that concrete steps are following:

(1) will be through filtering, cobalt concentration is that the cobalt chloride solution of 1～2 mol/L, pH value 4.75～5.20 is inserted in the reaction kettle;

(2) under agitation condition, the solution in the heating steps (1) makes the solution system temperature be controlled at 55～65 ℃, and keeps system temperature relatively stable;

(3) will filter in advance and concentration is that the ammonium bicarbonate soln of 1.8～2.5 mol/L at the uniform velocity sprays to the system of step (2) with the flow of 250～800L/h;

(4) solution system pH value 7.0～7.5 promptly stops the interpolation of ammonium bicarbonate soln as the system reaction end in the controlled step (3);

(5) with 20～40 minutes after-filtration of step (4) gained solid-liquid system ageing, repetitive scrubbing promptly gets material requested.