CN103342394B

CN103342394B - Method for continuously preparing cobalt hydroxide with high bulk density

Info

Publication number: CN103342394B
Application number: CN201310290589.9A
Authority: CN
Inventors: 徐伟; 田礼平; 刘茨梅; 王宁
Original assignee: Zhejiang Huayou Cobalt Co Ltd
Current assignee: Zhejiang Huayou Cobalt Co Ltd
Priority date: 2013-07-10
Filing date: 2013-07-10
Publication date: 2015-03-25
Anticipated expiration: 2033-07-10
Also published as: CN103342394A

Abstract

The invention discloses a method for continuously preparing cobalt hydroxide with high bulk density. The current cobalt hydroxide preparation methods include an alkali solution sedimentation method, a sedimentation conversion method and the like which have the following three difficulties: cobalt hydroxide sedimentation particles are smaller, difficult to filter and wash, and the recovery rate of materials is low; the materials are low in quality and high in impurity content; the high energy consumption is caused by intermittent production. The technical scheme is as follows: the method is characterized by comprising the following steps of: with cobalt-contained ore material as the raw material, leaching the cobalt-contained ore material, and then, purifying the cobalt-contained ore material to obtain a cobalt chloride solution; with NaOH as a base solution, merging NaOH, cobalt chloride and a complexing agent solution, adding the mixed solution into a reaction kettle, rapidly controlling the pH value at 8-12, the temperature at 30-90 DEG C and the stirring speed at 200-1000rpm in the flow merging process, and opening an overflow valve of the reaction kettle to begin to carry out continuous production after the reaction is carried out for 6-40h. The method is simple in process, capable of realizing continuous production, convenient in operation and beneficial to the industrial production; a product is excellent and is shaped like a porous sphere, and the particle size of the product is distributed normally.

Description

The method of high pine than cobalt hydroxide is prepared in a kind of serialization

Technical field

The present invention relates to a kind of serialization and prepare the method for high pine than cobalt hydroxide.

Background technology

Cobalt hydroxide is a kind of important raw material of industry, for the manufacture of cobalt salt in Chemical Manufacture, cobalt-containing catalyst and the agent of electrolysis production decomposing hydrogen dioxide solution, coatings industry is used as paint drier, glass is warded off industry and is used as colouring agent etc., at battery industry for the manufacture of MH-Ni, lithium ion battery.Along with the fast development of China's economic society, the parent that green energy resource is subject to people relies, and battery industry grows continuously and fast, and the application of cobalt hydroxide is constantly expanded in addition, and the demand in market is also increasing.

Method prepared by the cobalt hydroxide of present has the alkali lye precipitation method, precipitation transformation method etc.There are three difficult problems in current technology: (1) cobalt hydroxide deposit seed is less, sad filter aborning, difficult washing, and material recovery rate is low; (2) materials quality is poor, and impurity content is high; (3) batch production, energy consumption is high.

The patent of invention CN1359353 of OMG Kokkola Chemicals OY and domestic patent CN101570348A needs to add the ammonia alkali such as ammoniacal liquor, and in product, impurity content is high, and waste water not easily processes.

The patent of invention CN1190947 of H.C. Starck GmbH & Co. KG discloses and adopts precipitation transformation method to prepare Large stone cobalt hydroxide, first cobalt salt and carbonate or bicarbonate is used to form basic cobaltous carbonate, after washing drying, basic cobaltous carbonate is pulled an oar, then mix with NaOH solution, after washing, product needs vacuum dehydrating at lower temperature.This method production process is long, and drying condition is harsh, is unfavorable for suitability for industrialized production.

Summary of the invention

The defect existed for above-mentioned technique and technical difficulty, the invention provides a kind of serialization and prepare the method for high pine than cobalt hydroxide, its technique is simple, and continuous prodution, easy to operate, product fine, is conducive to suitability for industrialized production.

For this reason, the present invention adopts following technical scheme: the method for high pine than cobalt hydroxide is prepared in a kind of serialization, and its step is as follows: adopting containing cobalt ore material is raw material, through leaching purification, obtains 30 ~ 200g/L cobalt chloride solution; Preparation 50 ~ 400g/L NaOH solution and 0.01 ~ 100g/L enveloping agent solution; Take NaOH as end liquid, by NaOH, cobalt chloride and enveloping agent solution and stream adds reactor, rapidly pH value is controlled 8 ~ 12 in co-current process, temperature controls at 30 ~ 90 DEG C, mixing speed at 200 ~ 1000rpm, reaction 6 ~ 40h after, open the overflow valve of reactor, start continuous prodution; The reaction material overflowed adds appropriate antioxidant, ageing 2 ~ 4h, namely obtains cobalt hydroxide after filtration, washing, drying.

The cobalt chloride that the present invention produces, its quality standard is: Co:30 ~ 200g/L, Cu < 0.001g/L, Mg < 0.001g/L, Fe < 0.001g/L, Ni < 0.001g/L, Ca < 0.001g/L, Mn < 0.001g/L, Zn < 0.001g/L, Na < 0.001g/L, Cd < 0.001g/L, Cr < 0.001g/L, Pb < 0.001g/L, Al < 0.001g/L.

The cobalt hydroxide excellent product quality that the present invention produces, pattern is porous spherical, and granularity is normal distribution, D50:8 ~ 20 μm, Na < 0.004%, Cl ^-< 0.025%, AD (pine ratio): 1.0 ~ 2.0g/cm ³.

Further, the control of reaction temperature, pH value, cocurrent adding material speed and mixing speed adopts DCS Distributed Control System to control, easy to operate.

Further, described complexing agent is preferably one or more mixture of PVP (PVP), polyvinyl alcohol (PVA), disodium ethylene diamine tetraacetate (EDTA), polyethylene glycol (PEG), sodium potassium tartrate tetrahydrate (rocchelle's salt).

Further, when cocurrent adding material, enveloping agent solution can add separately, also may be combined in cobalt chloride or NaOH solution and adds.

Further, described antioxidant is preferably one or more mixture of ascorbic acid, glucose, n-propyl gallate, hydroxyl hydramine.

Further, described filtration, washing process adopt centrifuge.

Present invention process is simple, continuous prodution, easy to operate, is conducive to suitability for industrialized production; Product fine, pattern is porous spherical, and granularity is normal distribution.

Accompanying drawing explanation

Fig. 1 is that cobalt hydroxide SEM prepared by the embodiment of the present invention 1 schemes.

Fig. 2 is that cobalt hydroxide SEM prepared by the embodiment of the present invention 2 schemes.

Detailed description of the invention

Below in conjunction with specification drawings and specific embodiments, the invention will be further described.

embodiment 1

Take NaOH as end liquid, by 60g/L NaOH, 100g/L cobalt chloride, 12g/L poly-vinyl alcohol solution, and stream adds reactor, rapidly pH value is controlled 10.0 in process, temperature controls at 30 ~ 90 DEG C, mixing speed 200 ~ 1000rpm, after reaction 6 ~ 40h, open overflow valve, start continuous prodution.The reaction material overflowed adds appropriate glucose, ageing 2 ~ 4h.After filtration, cobalt hydroxide can be obtained after washing, drying.

embodiment 2

Take NaOH as end liquid, 250g/L NaOH is mixed with 25g/L disodium ethylene diamine tetra-acetic acid solution, and with 150g/L cobalt chloride and stream adds reactor, rapidly pH value is controlled 10.5 in process, temperature controls at 30 ~ 90 DEG C, mixing speed 200 ~ 1000rpm, after reaction 6 ~ 40h, open overflow valve, start continuous prodution.The reaction material overflowed adds appropriate ascorbic acid, ageing 2 ~ 4h.After filtration, cobalt hydroxide can be obtained after washing, drying.

Claims

1. the method for high pine than cobalt hydroxide is prepared in serialization, and its step is as follows: adopting containing cobalt ore material is raw material, through leaching purification, obtains 30 ~ 200g/L cobalt chloride solution; Preparation 50 ~ 400g/L NaOH solution and 0.01 ~ 100g/L enveloping agent solution; Take NaOH as end liquid, by NaOH, cobalt chloride and enveloping agent solution and stream adds reactor, rapidly pH value is controlled 8 ~ 12 in co-current process, temperature controls at 30 ~ 90 DEG C, mixing speed at 200 ~ 1000rpm, reaction 6 ~ 40h after, open the overflow valve of reactor, start continuous prodution; The reaction material overflowed adds appropriate antioxidant, ageing 2 ~ 4h, namely obtains cobalt hydroxide after filtration, washing, drying;

Described complexing agent is one or more mixture of PVP, polyvinyl alcohol, disodium ethylene diamine tetraacetate, polyethylene glycol, sodium potassium tartrate tetrahydrate.

2. serialization according to claim 1 prepares high pine than the method for cobalt hydroxide, it is characterized in that, the control of reaction temperature, pH value, cocurrent adding material speed and mixing speed adopts DCS Distributed Control System to control.

3. serialization according to claim 1 and 2 prepares high pine than the method for cobalt hydroxide, it is characterized in that, when cocurrent adding material, enveloping agent solution adopts to add separately or be blended in cobalt chloride or NaOH solution and adds.

4. the method for high pine than cobalt hydroxide is prepared in serialization according to claim 1 and 2, and it is characterized in that, described antioxidant is one or more mixture of ascorbic acid, glucose, n-propyl gallate, hydroxyl hydramine.

5. serialization according to claim 1 and 2 prepares high pine than the method for cobalt hydroxide, and it is characterized in that, described filtration and washing process adopt centrifuge.