CN1242976C

CN1242976C - Technology process for synthetic oragnocobalt solt

Info

Publication number: CN1242976C
Application number: CN 200310105264
Authority: CN
Inventors: 颜秉舟; 于立珍; 王心满
Original assignee: Individual
Current assignee: Individual
Priority date: 2003-12-02
Filing date: 2003-12-02
Publication date: 2006-02-22
Anticipated expiration: 2023-12-02
Also published as: CN1623972A

Abstract

The present invention relates to an organic cobalt salt synthesis method which generates a basic cobaltous carbonate intermediate by the reaction of inorganic cobalt salts of cobalt sulfate, etc. with sodium carbonate and water. The present invention is characterized in that wet basic cobaltous carbonate directly reacts with solvent oil and organic acid to synthesize organic cobalt salt, the reaction temperature is 40 to 230 DEG C, and the reaction time is 16 to 24 hours; in order to raise the reaction speed, organic acid of stoichiometric amount is put in by 2 to 4 times, and the hydrous intermediate is emulsified in the solvent oil into particle blocks; in the heating-up reaction process, water and solvents are removed in a reflux mode, the water removal reflux temperature is 90 to 160 DEG C, and the oil removal reflux temperature is 160 to 230 DEG C. The present invention changes the dry method synthesis of organic cobalt salt into direct synthesis of organic cobalt salt by wet basic cobaltous carbonate filtration substances, which omits the processes of drying, grinding and packing, decreases equipment investment and has the advantages of advanced and reasonable process and short production periodicity.

Description

Process for synthesizing organic cobalt salt

The present invention relates to a preparation method of organic cobalt salt, in particular, it relates to a preparation process for synthesizing organic cobalt salt by using inorganic cobalt salt of cobalt sulfate or cobalt chloride, etc. as raw material.

The traditional method for synthesizing organic cobalt salt is a dry synthesis method, i.e. firstly, using inorganic cobalt salt of cobalt sulfate or cobalt chloride and soda ash to prepare basic cobalt carbonate, then washing and drying to prepare cobalt powder, then using the basic cobalt carbonate and organic acid to synthesize cobalt salt adhesive.

The task of the invention is to design a new process: the wet process for synthesizing organic cobalt salt is characterized by that the produced basic cobalt carbonate intermediate is directly fed into reaction still to synthesize organic cobalt salt without drying process, and said process has no need of drying process, so that it features short technological process, less equipment investment and short production period.

The invention is characterized in that the method adopts an emulsification dispersion technology, namely, utilizes the emulsification function of the generated organic cobalt to directly synthesize the organic cobalt salt with the generated basic cobaltouscarbonate intermediate filter cake and organic acid in a solvent oil medium without drying. The synthesis process of the invention comprises the following steps:

1. synthesis of basic cobalt carbonate

The basic cobaltous carbonate is prepared by adding water into soda and cobaltous sulfate for reaction, and the reaction equation is as follows:

and washing the basic cobaltous carbonate intermediate generated by the reaction to be neutral, and performing filter pressing to obtain a wet basic cobaltous carbonate filter cake.

2. Synthesis of organic cobalt salts

Directly putting the basic cobaltous carbonate filter cake, the organic acid and the solvent oil into a reaction kettle to synthesize the organic cobalt salt, wherein the reaction temperature is 40-230 ℃, and the reaction time is 16-24 hours; in order to accelerate the reaction speed and timely dewater during synthesis, solvent oil is added as a reaction medium, water-containing wet filter cakes are aggregated in an oil phase and are difficult to disperse, the water-containing wet filter cakes are not easy to contact with organic acid, and the synthesis reaction is difficult to carry out, so that the emulsifying function of the generated organic cobalt salt is utilized, the organic acid with stoichiometric amount is added for 2-4 times during feeding, the water-containing filter cakes are emulsified and dispersed in the solvent oil into small particle blocks below 5mm under the shearing force action of a stirring propeller, and a water-in-oil and filter cake system is formed under the action of the organic acid or the organic acid cobalt surfactant. When the reaction temperature reaches 90 ℃ and the reaction time exceeds 4 hours, the water and the solvent oil in the reaction kettle form an azeotrope, the azeotrope begins a dehydration reflux process, the azeotrope enters a solvent oil storage tank after condensation, the lower layer of water is discharged after layering, the upper layer of solvent oil is refluxed and recycled, the dehydration reflux temperature is 90-160 ℃, the entrained water of the intermediate basic cobalt carbonate is removed, and the reaction product water of the synthetic organic cobalt salt is generated; if reduced pressure distillation is adopted, the time for dehydration and solvent oil can be shortened by 2-4 hr when the vacuum degree reaches-0.05 to-0.1 Mpa. And when the reaction temperature reaches 160-230 ℃, the reflux process of the desolventizing oil is carried out, the dehydration and the desolventizing are carried out in the whole temperature-rising reaction process, the solvent oil is completely removed at 220-230 ℃, and the solvent oil enters a solvent oil receiving storage tank for recycling through condensation, so that the organic cobalt salt product is finally obtained.

The organic acid adopted by the invention is various organic acids of C2-C18, one or a plurality of mixtures thereof are selected, and the organic acids comprise: glacial acetic acid, propionic acid, naphthenic acid, pivalic acid, isooctanoic acid, abietic acid, nonacarbonic acid, decacarbonic acid, stearic acid, butyric acid, etc.; the solvent oil can be selected from toluene, xylene solvents and 80-200 # solvent gasoline. The adding amount of the solvent oil to the theoretical amount of the generated organic cobalt salt is 1: 1 (weight).

The further process conditions for synthesizing the organic cobalt salt comprise the following steps: the reaction temperature is in the range of 40-80 ℃ for 2-4 hours, and the reaction temperature is in the range of 80-120 ℃ for 10-14 hours. Feeding organic acid twice, wherein the weight of the organic acid is 20-50% of the total amount of the organic acid, and the rest amount of the organic acid is fed when the reaction time reaches 2 hours and the temperature is 60-80 ℃ for the second time; the organic acid is fed for three times, wherein the weight of the organic acid is 20-30% of the total amount of the materials, the organic acid is fed for the second time when the reaction time reaches 2 hours and the temperature is 60-80 ℃, the organic acid is fed for 20-50% of the total amount of the materials, and the organic acid is fed for the third time when the reaction time reaches 4 hours and the temperature is 80-90 ℃, wherein the rest amount of the organic acid is left. The particle size of the basic cobaltous carbonate filter in the reaction process of synthesizing organic cobalt salt is controlled below 5 mm.

The invention has the advantages of shortened process flow, reduced equipment investment, advanced process, short production period of products and the like.

The following description is made with reference to the accompanying drawings in which embodiments of the present invention are shown.

FIG. 1 is a flow chart of a conventional dry synthesis process.

FIG. 2 is a flow chart of a process for synthesizing organic cobalt salt by a wet method.

Example 1:

taking CoSO₄(cobalt sulfate) with Na₂CO₃Reacting (industrial sodium carbonate) in an aqueous solution according to a molar ratio of 1: 1 to generate basic cobalt carbonate precipitate, wherein the reaction pH value is 10-11, the reaction concentration is 17-54% (by weight), the reaction temperature is 40-95 ℃, the generated basic cobalt carbonate is washed by water to be neutral, and the basic cobalt carbonate precipitate is subjected to pressure filtration for later use when the pH value is less than or equal to 8; taking naphthenic acid, isooctanoic acid, abietic acid and acetic acid (the total mole number of the mixed acid is 4) and 1 mole of basic cobalt carbonate intermediateAnd (3) reacting, wherein the particle size of the basic cobalt carbonate filter material in the reaction process of synthesizing the organic cobalt salt is controlled to be less than 5 mm. The solvent oil is xylene, and the adding amount of the xylene and the theoretical generation amount of the organic cobalt salt are 1: 1 (weight ratio). When the temperature is raised to 40 ℃, 40 percent of the total weight of the mixed acid is added; the reaction temperature is 60-80 ℃, the reaction time is 2 hours, and the residual amount of the mixed acid is added; when the reaction temperature is 90 ℃, dehydrating and refluxing are started, the refluxing time is 10-14 hours, the solvent removal is started when the temperature is above 160 ℃, the refluxing time is 4-6 hours, and when the temperature is 220 +/-5 ℃, the solvent is completely removed; then cooling to 160 +/-5 ℃, adding propyl borate, adding 1/6 of the molar number of the basic cobalt carbonate, and removing propyl acetate generated by reaction to finally obtain the product of cobalt boracylate.

Example 2:

the basic cobalt carbonate intermediate was prepared as in example 1. Taking stearic acid, basic cobaltous carbonate and No. 170 solvent gasoline, wherein the adding amount of the gasoline and the theoretical generating amount of organic cobalt salt are 1: 1 (weight ratio), and the particle block of the basic cobaltous carbonate filter in the reaction process of synthesizing the organic cobalt salt is controlled below 5 mm; when the temperature is raised to 40 ℃, 20 percent of the total amount of stearic acid is added, the reaction time reaches 2 hours, when the reaction temperature reaches 70 +/-2 ℃, 40percent of the total amount of acid is added, and when the reaction temperature reaches 85 +/-2 ℃, the reaction time reaches 4 hours, the residual amount of the total amount of stearic acid is added. The technological conditions of dehydration and desolventizing oil are the same as those of the example 1, and finally the product of cobalt stearate is obtained.

Example 3:

the basic cobalt carbonate intermediate was prepared as in example 1. Taking isooctanoic acid, basic cobaltous carbonate (mol ratio) 4: 1 and No. 120 solvent gasoline, wherein the adding amount of the gasoline and the theoretical generating amount of organic cobalt salt (weight ratio) 1: 1; when the temperature is raised to 40 ℃, 40 percent of the total amount of the isooctanoic acid is added, the reaction time reaches 2 hours, when the reaction temperature is 60 +/-2 ℃, 60 percent of the total acid is added, the technological conditions of dehydration and solvent removal oil are the same as those of the example 1, and finally the product cobalt isooctanoic acid is obtained.

Claims

1. A process for synthesizing organic cobalt salt includes such steps as reaction of inorganic cobalt salt (cobalt sulfate or cobalt chloride), sodium carbonate and water to obtain basic cobalt carbonate intermediate, water washing to neutrality, and features that:

a) directly reacting wet basic cobaltous carbonate with solvent oil and organic acid to synthesize organic cobalt salt, wherein the reaction temperature is 40-230 ℃, and the reaction time is 16-24 hours;

b) adding the organic acid according to the stoichiometric amount for 2-4 times,

c) refluxing to remove water and solvent oil in the temperature rise reaction process, wherein the dehydration reflux temperature is 90-160 ℃, and the desolventizing oil reflux temperature is 160-230 ℃.

2. The process according to claim 1, wherein the organic acid is C₂～C₁₈The solvent oil is toluene, xylene solvent and 80-200 # gasoline.

3. The process of claim 2 wherein the organic acid is one or more of glacial acetic acid, propionic acid, naphthenic acid, isooctanoic acid, stearic acid, pivalic acid, abietic acid, nonacarbonic acid, decacarbonic acid, and butyric acid.

4. The process according to claim 1, wherein the reaction temperature is 40 to 80 ℃ and the reaction time is 2 to 4 hours and 80 to 120 ℃ and 10 to 14 hours.

5. A process according to claim 1, wherein the organic acid is added in 2 portions, the first portion is 20-50% of the total amount of the materials, and the second portion is added with the rest amount when the reaction time reaches 2 hours and the temperature is 60-80 ℃.

6. A process according to claim 1, wherein the organic acid is added in 3 portions, the first portion is 20-30% of the total amount, the second portion is 20-50% of the total amount when the reaction time reaches 2 hours and the temperature reaches 60-80 ℃, and the third portion is 4 hours and the temperature reaches 80-90 ℃.

7. A process according to claim 1 or 2, wherein the weight ratio of the mineral spirit to the theoretical amount of organocobalt salt formed is 1: 1.

8. A process according to claim 1, wherein the particle size of the basic cobalt carbonate filtrate during the reaction for synthesizing the organic cobalt salt is controlled to be less than 5 mm.