CN1206201C - Preparation method of cobalt acetate and cobalt oxalate - Google Patents
Preparation method of cobalt acetate and cobalt oxalate Download PDFInfo
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- CN1206201C CN1206201C CN03139007.2A CN03139007A CN1206201C CN 1206201 C CN1206201 C CN 1206201C CN 03139007 A CN03139007 A CN 03139007A CN 1206201 C CN1206201 C CN 1206201C
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Abstract
The invention relates to the field of preparation methods of cobalt acetate and cobalt oxalate. Adding industrial grade metal cobalt which is not subjected to any ultrafine dispersion treatment into a reactor with a heating and condensing device, and uniformly injecting acetic acid peroxide or hydrogen peroxide, acetic acid and water into the reactor from a feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or flow guide device, wherein the concentration of the acetic acid peroxide is 0.5-20% or the concentration of the hydrogen peroxide is 0.2-10%, and the concentration of the acetic acid is 3-40%. The reaction temperature is adjusted to 50-140 ℃ and the pressure is 5 multiplied by 104Pa～4.0×105Pa, continuously discharging the generated cobalt acetate salt solution from the bottom of the reactor, wherein the solution does not contain nitrate and chloride, and can be directly used as a high-activity catalyst for preparing aromatic carboxylic acid by liquid-phase oxidation of aromatic hydrocarbon or used for preparing high-purity crystal cobalt acetate by filtering; directly adding oxalic acid into the obtained cobalt acetate solution to obtain cobalt oxalate precipitate, wherein the molar ratio of the oxalic acid to the cobalt acetate is 1: 0.8-1.2, and separating the precipitateWashing and drying to obtain high-purity cobalt oxalate, and recovering the solution for producing cobalt acetate.
Description
Technical Field
The invention relates to the field of preparation methods of cobalt acetate and cobalt oxalate. More particularly to a method for preparing cobalt acetate by directly reacting metal cobalt with peroxyacetic acid or hydrogen peroxide and acetic acid solution and preparing cobalt oxalate by directly reacting cobalt acetate with oxalic acid.
Background
95110509.4 discloses a method for preparing cobalt acetate by directly reacting metallic cobalt with acetic acid and hydrogen peroxide, which is characterized in that metallic cobalt is added into a column-shaped or tank-shaped reactor, acetic acid and oxidant hydrogen peroxide are added into the top of the reactor, and simultaneously cobalt acetate solution is continuously discharged from the bottom of the reactor to prepare cobalt acetate.
95110509.4 has one of the disadvantages that the reaction liquid is in contact reaction with the metal cobalt only by self gravity in the reaction, the mass transfer speed is slow, the side reaction is intensified, the utilization rate of the hydrogen peroxide is low, and the method is more obvious when the process productivity is improved by improving the feeding speed of the hydrogen peroxide; furthermore, as the hydrogen peroxide concentration increases, e.g., above 3%, the hydrogen peroxide utilization decreases significantly.
95110509.4 has the disadvantage of no consideration of pressure and temperature, and significantly reduced utilization rate of hydrogen peroxide.
95110509.4 is that there is a disadvantage of being smaller for a specific surface area (less than 0.4 cm)2The technical cobalt metal,/g), did not investigate the reaction behavior.
95110509.4 the fourth disadvantage is that the utilization rate of hydrogen peroxide and the process productivity are not considered, and the utilization rate of hydrogen peroxide is too low, which leads to the increase of production cost and neglects the requirement of practicability.
94111509.7A process for preparing cobalt oxalate features that the metallic cobalt is dissolved in sulfuric acid and nitric acid, and then oxalic acid and ammonia are added to obtain cobalt oxalate.
94111509.7 one of the disadvantages is that the process is complex, after the metal cobalt is dissolved by sulfuric acid and nitric acid, the cobalt oxalate is obtained after the processes of crystallization, redissolution, temperature rise, impurity removal, neutralization, precipitation and the like.
94111509.7 the disadvantage is that the cobalt salt reacts with oxalate to produce cobalt oxalate with a large amount of by-products such as ammonium sulfate, ammonium chloride and a small amount of ammonium nitrate, which requires a large amount of water to wash the product.
94111509.7 the existence of significant NO or NO is a disadvantage2Gas and waste water environmental pollution.
Disclosure of Invention
One of the purposes of the invention is to overcome the disadvantages of patent 95110509.4, and to adopt new technical characteristics to promote the full contact and reaction of liquid and solid, improve the utilization rate of hydrogen peroxide and give consideration to the productivity; the second purpose of the invention is to provide a method for preparing cobalt acetate by directly reacting peroxyacetic acid with metallic cobalt; the invention also aims to overcome the defect of 94111509.7 and provide a method for preparing cobalt oxalate by directly reacting cobalt acetate with oxalic acid.
In order to achieve the purpose of the invention, the top of the reactor is provided with a liquid spray header or a spray pipe to promote the distribution or the flow guide of reaction liquid and promote the reaction liquid to accelerate the mass transfer process by adjusting the reaction temperature and the reaction pressure, thereby reducing the decomposition of peroxide caused by uneven dispersion, long mass transfer time or slow reaction speed of the reaction liquid; researching and investigating the reaction behavior of the peroxyacetic acid and the metal cobalt; directly uses industrial grade metal cobalt as a raw material, and gives consideration to the utilization rate of hydrogen peroxide and the process productivity; the method is characterized in that oxalic acid is directly added into the obtained cobalt acetate solution to prepare the cobalt oxalate by means of the characteristics that the reaction solution passivates main impurities of copper and nickel in the cobalt in the preparation process of the cobalt acetate and the impurity content in the generated cobalt acetate solution is low.
The invention is described in detail below:
the method comprises the steps of adding metal cobalt into a reactor with a heating and condensing device, injecting acetic acid peroxide or hydrogen peroxide, acetic acid and water into the reactor from a reactor feed inlet positioned at the upper part of the metal cobalt through a liquid distribution or diversion device, wherein the concentration of the acetic acid peroxide is 0.5-20% or the concentration of the hydrogen peroxide is 0.2-10%, the concentration of the acetic acid is 3-40%, adjusting the heating and condensing device on the reactor to keep the temperature of the reactor between 50-140 ℃, and the pressure of the reactor is 5 multiplied by 104Pa～4.0×105Pa, promoting the reaction of metal cobalt and acetic acid peroxide or hydrogen peroxide and acetic acid to convert into cobalt acetate, discharging the generated cobalt acetate salt solution through the bottom of the reactor, filtering the solution by a filter, and directly preparing a catalyst for preparing aromatic carboxylic acid by oxidizing aromatic hydrocarbon in a liquid phase or preparing crystal cobalt acetate or other cobalt salts by crystallization.
Adding the cobalt acetate salt solution obtained in the process into another reactor, directly adding industrial oxalic acid, controlling the molar ratio of oxalic acid to cobalt acetate to be 1: 0.8-1.2, stirring for 10-15 minutes, standing, cooling to normal temperature, filtering and separating out generated cobalt oxalate precipitate to obtain cobalt oxalate tetrahydrate, further drying at 100 +/-5 ℃ to obtain cobalt oxalate dihydrate, and recovering the filtrate for preparing a raw material solution for preparing cobalt acetate.
When the concentration of the peroxyacetic acid is lower than 0.5 percent or the concentration of the hydrogen peroxide is lower than 0.2 percent and the concentration of the acetic acid is lower than 3 percent, the method for preparing the cobalt acetate can easilykeep the utilization rate of the peroxyacetic acid or the hydrogen peroxide at 100 percent, but because the process productivity is too low, the concentration of the cobalt acetate in the obtained solution is lower, the cobalt acetate is not suitable to be directly used as a catalyst and is used for preparing the crystal cobalt acetate or other cobalt salts, the production efficiency is low, and the energy consumption is high; when the concentration of the peroxyacetic acid is higher than 20 percent or the concentration of the hydrogen peroxide is higher than 10 percent and the concentration of the acetic acid is higher than 40 percent, a large number of black particles are generated in the solution along with the increase of the concentration of the peroxide, the concentration of the cobalt acetate generated by the reaction is not obviously changed, and the utilization rate of the peroxyacetic acid or the hydrogen peroxide is reduced, so that the concentration of the peroxyacetic acid is 0.5-20 percent or the concentration of the hydrogen peroxide is 0.2-10 percent and the concentration of the acetic acid is 3-40 percent.
The preparation method of the cobalt acetate provided by the invention has the advantages that the reaction temperature is kept between 50 and 140 ℃ and the pressure is kept at 5.0 multiplied by 10 by adjusting the heating and condensing device on the reactor4Pa～4.0×105Pa, when the temperature in the cobalt acetate synthesis reactor is lower than 50 ℃ or the pressure is lower than 5.0 multiplied by 104When Pa, the reaction speed is slow, the reaction is incomplete, the utilization rate of the peroxyacetic acid or the hydrogen peroxide and the acetic acid is low, and the production rate of the cobalt acetate is also low; when the temperature is higher than 140 ℃ or the pressure exceeds 4.0X 105When Pa is needed, the acetic acid peroxide or hydrogen peroxide self-decomposition side reaction is intensified, a large amount of heat and gas are generated at the same time, the utilization rate of the acetic acid peroxide or hydrogen peroxide and acetic acid is reduced, and the technical requirement on equipment is increased, so that the reaction temperature is controlled to be 50-140 ℃, and the reaction pressure is controlled to be 5.0 multiplied by 104Pa～4.0×105Pa。
The preparation method of the cobalt acetate can effectively give consideration to the utilization rate of the acetic peroxide or the hydrogen peroxide and the production rate of the cobalt acetate by controlling the concentrations of the acetic peroxide or the hydrogen peroxide and the acetic acid and controlling the feeding speed of the reaction liquid.
The preparation method of the cobalt oxalate comprises the steps of directly adding oxalic acid into a cobalt acetate solution, reacting the cobalt acetate with the oxalic acid to generate cobalt oxalate precipitate, releasing acetic acid, and recovering the solution for preparing the cobalt acetate after filtering or centrifugally separating the cobalt oxalate.
According to the preparation method of the cobalt oxalate, the cobalt oxalate precipitate can be obtained through the excess of the oxalic acid or the excess of the cobalt acetate. However, when the molar ratio of oxalic acid to cobalt acetate is greater than 1: 0.8, a relatively large amount of oxalic acid remains in the solution after the precipitation is completed; when the molar ratio of oxalic acid to cobalt acetate is less than 1: 1.2, a large amount of cobalt ions are remained in the solution after the precipitation is finished; the invention generally controls the molar ratio of the oxalic acid to the cobalt acetate to be 1: 0.8-1.2, and the solution obtained after separation and precipitation is more convenient to recycle.
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples:
example 1: in a reactor having a volume of 500ml (an effective volume of about 377ml), 800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged, the nickel content in the cobalt being 0.3%. Injecting acetic acid peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 105g/min, the concentration of the acetic acid peroxide is 0.5 percent, the concentration of the acetic acid is 3 percent, the reaction temperature is kept at 135 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the reactor pressure is (4.0 +/-0.2) multiplied by 105Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 274g/l.h, and the utilization rate of the acetic peroxide is 100%.
Example 2: in a reactor having a volume of 500ml (an effective volume of about 377ml), 800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged, the nickel content in the cobalt being 0.3%. Injecting acetic acid peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 100g/min, the concentration of the acetic acid peroxide is 2 percent, the concentration ofthe acetic acid is 6 percent, and the reaction temperature is kept at 120 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the reactor pressure is (2.5 +/-0.2) multiplied by 105Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 960g/l.h, and the utilization rate of the acetic peroxide is 92%.
Example 3
800g of a reactor having a volume of 500ml (effective volume of about 377ml) and connected to a vacuum system at the outlet thereof was charged without any excessThe finely dispersed industrial grade metal cobalt has a nickel content of 0.3 percent. Injecting acetic acid peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 80g/min, the concentration of the acetic acid peroxide is 5 percent, the concentration of the acetic acid is 6 percent, the reaction temperature is kept at 90 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the vacuum degree is adjusted to be (6.0 +/-0.2) multiplied by 104Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 1732g/l.h, and the utilization rate of the acetic peroxide is 83%.
Example 4
800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged into a reactor having a volume of 500ml (an effective volume of about 377ml) and a vacuum system connected to the discharge port, the nickel content in the cobalt being 0.3%. To oxidize oxygenInjecting the acetic acid, acetic acid and water into the reactor from the inlet of the reactor at the upper part of the metal cobalt layer by a liquid distribution or diversion device at a feeding speed of 75g/min, a concentration of the peroxyacetic acid of 5% and a concentration of the acetic acid of 10%, maintaining the reaction temperature at 90 + -5 deg.C by adjusting the heating and condensing device on the reactor, and adjusting the vacuum degree at (6.0 + -0.2) × 10 deg.C4Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 1663g/l.h, and the utilization rate of the acetic peroxide is 85%.
Adding 200g of cobalt acetate salt solution into another reactor, adding 16.95g of industrial grade oxalic acid, wherein the molar ratio of the oxalic acid to the cobalt acetate is 1: 0.8, stirring for 10-15 minutes, standing, cooling to normal temperature, filtering to separate out cobalt oxalate precipitate to obtain cobalt oxalate tetrahydrate, and further drying at 100 +/-5 ℃ to obtain cobalt oxalate dihydrate, wherein the product quality meets the requirement of analytical purity standard. The filtrate is recovered and returned to be used for preparing the raw material liquid for preparing the cobalt acetate.
Example 5
Adding 800g of industrial grade metal cobalt without any ultrafine dispersion treatment into a reactor with the volume of 500ml (the effective volume is about 377ml), wherein the content of nickel in the cobalt is 0.3%, adding 80g of metal nickel into the reactor, injecting peracetic acid, acetic acid and water into the reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 100g/min, the concentration of the peracetic acid is 5%, the concentration of the acetic acid is 10%, and keeping the reaction temperature at 100 +/-5 ℃ by adjusting a heating and condensing device on the reactor, wherein the pressure of the reactor is 1.0 x 10 at the moment5Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 2034g/l.h, and the utilization rate of the acetic peroxide is 78%.
Example 6
In a reactor having a volume of 500ml (an effective volume of about 377ml), 800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged, the nickel content in the cobalt being 0.3%. Injecting acetic acid peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 80g/min, the concentration of the acetic acid peroxide is 12 percent, the concentration of the acetic acid is 15 percent, the reaction temperature is kept at 50 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the reactor pressure is 1.0 multiplied by 105Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 3605g/l.h, and the utilization rate of the acetic peroxide is 72%.
Example 7
Into a reactor having a volume of 500ml (effective volume about 377ml) was charged 800g of technical grade metallic cobalt without any ultrafine dispersion treatment, cobaltThe content of nickel in the alloy is 0.3 percent. Injecting acetic acid peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 80g/min, the concentration of the acetic acid peroxide is 12 percent, the concentration of the acetic acid is 18 percent, the reaction temperature is kept at 60 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the reactor pressure is 1.0 multiplied by 105Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 3655g/l.h, and the utilization rate of the acetic peroxide is73％。
Example 8
800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged into a reactor having a volume of 500ml (an effective volume of about 377ml) and a vacuum system connected to the discharge port, the nickel content in the cobalt being 0.3%. Injecting the acetic acid peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 65g/min, the concentration of the acetic acid peroxide is 20 percent, the concentration of the acetic acid is 25 percent, the reaction temperature is kept at 95 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the vacuum degree is adjusted to be (8.0 +/-0.2) multiplied by 101Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 4204g/l.h, and the utilization rate of the acetic peroxide is 62%.
Example 9
In a reactor having a volume of 500ml (an effective volume of about 377ml), 800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged, the nickel content in the cobalt being 0.3%. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feed speed is 105g/min, the concentration of the hydrogen peroxide is 0.2 percent, and the acetic acid is concentratedThe temperature is 2%, the reaction temperature is kept at 125 + -5 ℃ by adjusting a heating and condensing device on the reactor, and the pressure of the reactor is (3.0 + -0.2) multiplied by 105Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 245g/l.h, and the utilization rate of the hydrogen peroxide is 100%.
Example 10
800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged into a reactor having a volume of 500ml (an effective volume of about 377ml) and a vacuum system connected to the discharge port, the nickel content in the cobalt being 0.3%. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 70g/min, the concentration of the hydrogen peroxide is 2.5 percent, the concentration of the acetic acid is 10 percent, the reaction temperature is kept at 100 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the vacuum degree is adjusted to be (8.0 +/-0.2) multiplied by 104Pa, continuously discharging the generated cobalt acetate salt solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 1754g/l.h, and the utilization rate of the hydrogen peroxide is 86%.
Example 11
800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged into a reactor having a volume of 500ml(an effective volume of about 377ml) and a vacuum system connected to the discharge port, the nickel content in the cobalt being 0.3%. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feed speed is 105g/min, the concentration of the hydrogen peroxide is 2.5 percent, the concentration of the acetic acid is 10 percent, keeping the reaction temperature at 100 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and adjusting the vacuum degree to be (5.0 +/-0.2) multiplied by 104Pa, continuously discharging the generated cobalt acetate salt solution from the bottom of the reactor, filtering,samples are taken for determination, the product quality meets the requirements of Chinese GB1290-77 and HG/T2302-1999 standard, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirement, and the production rate of the cobalt acetate is2326g/l.h, the utilization rate of hydrogen peroxide is 76%.
Example 12
800g of technical grade metallic cobalt without any ultrafine dispersion treatment, with a nickel content of 0.3%, were charged into a reactor having a volume of 500ml (an effective volume of about 377ml), and 80g of metallic nickel and 50g of metallic copper were further charged into the reactor. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 70g/min, the concentration of the hydrogen peroxide is 3 percent, the concentration of the acetic acid is 12 percent, and the reaction temperature is kept at 85 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the reactor pressure is 1.0 multiplied by105Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content still lower than the standard requirements, the productivity of the cobalt acetate is 1959g/l.h, and the utilization rate of the hydrogen peroxide is 80%.
Example 13
800g of technical grade metallic cobalt without any ultrafine dispersion treatment, with a nickel content of 0.3%, were charged into a reactor having a volume of 500ml (an effective volume of about 377ml), and 80g of metallic nickel were further charged into the reactor. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device at a feed speed of 120g/min, a hydrogen peroxide concentration of 3% and an acetic acid concentration of 12%, and adjusting a heating and condensing device on the reactor to keep the reaction temperature at 85 +/-5 ℃ at the moment that the reactor pressure is 1.0 multiplied by 105Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, taking samples for determination, and ensuring that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content still lower than the standard requirements, and the cobalt acetate solution does not contain nitrate, chloride and nickelThe productivity of (2) was 2812g/l.h, and the utilization rate of hydrogen peroxide was 67%.
Adding 200g of cobalt acetate salt solution into another reactor, adding 11.97g of industrial grade oxalic acid, wherein the molar ratio of the oxalic acid to the cobalt acetate is 1: 1.2, stirring for 10-15 minutes, standing, cooling to normal temperature, filtering to separate out cobalt oxalate precipitate to obtain cobalt oxalate tetrahydrate, and further drying at 100 +/-5 ℃ to obtain cobalt oxalate dihydrate, wherein the product quality meets the requirement of analytical purity standard. The filtrate is recovered and returned to be used for preparing the raw material liquid for preparing the cobalt acetate.
Example 14
In a reactor having a volume of 500ml (an effective volume of about 377ml), 800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged, the nickel content in the cobalt being 0.3%. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device at a feed speed of 80g/min, a hydrogen peroxide concentration of 5% and an acetic acid concentration of 20%, and adjusting a heating and condensing device on the reactor to keep the reaction temperature at 135 +/-5 ℃ at the moment that the reactor pressure is (4.0 +/-0.2) multiplied by 105Pa, continuously discharging the generated cobalt acetate salt solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 3451g/l.h, and the utilization rate of the hydrogen peroxide is 74 percent.
Example 15
In a reactor having a volume of 500ml (an effective volume of about 377ml), 800g of technical grade metallic cobalt without any ultrafine dispersion treatment was charged,the nickel content in the cobalt being 0.3%. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 70g/min, the concentration of the hydrogen peroxide is 10 percent, the concentration of the acetic acid is 40 percent, and heating and cooling on the reactor are adjustedCondensing unit to maintain the reaction temperature at 50 + -5 deg.C under the reactor pressure of 1.0 × 105Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, measuring a sample, and producingThe quality of the product meets the requirements of Chinese GB1290-77 and HG/T2302-1999 standards, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the productivity of the cobalt acetate is 4733g/l.h, and the utilization rate of the hydrogen peroxide is 58%.
Example 16
250kg of technical grade metallic cobalt without any ultrafine dispersion treatment (specific surface area<4.0 cm) were charged into a reactor having an effective volume of 80l2In a ratio of<1 cm/g2At least 80% of metallic cobalt in the per gram, the minimum specific surface area of the metallic cobalt is less than 0.09cm2In terms of/g), the nickel content in the cobalt is 0.3%. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device at a feed speed of 500kg/h, a hydrogen peroxide concentration of 5% and an acetic acid concentration of 20%, and adjusting a heating and condensing device on the reactor to keep the reaction temperature at 90 +/-5 ℃ at the moment that the reactor pressure is 1.0 multiplied by 105Pa, continuously discharging the generated cobalt acetate salt solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 1717g/l.h, and the utilization rate of the hydrogen peroxide is 75 percent.
Example 17
250kg of the same technical grade metallic cobalt as in example 16 were charged into a reactor having an effective volume of 80 l. Injecting hydrogen peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device at a feed rate of 900kg/h, a hydrogen peroxide concentration of 2.5% and an acetic acid concentration of 12%, and adjusting a heating and condensing device on the reactor to keep the reaction temperature at 100 +/-5 ℃ at the moment that the reactor pressure is 1.0 x 105Pa, continuously discharging the generated cobalt acetate salt solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 1607g/l.h, and the utilization rate of the hydrogen peroxide is 78%.
Adding 100kg of cobalt acetate salt solution into another reactor, adding 7.35kg of industrial grade oxalic acid, wherein the molar ratio of the oxalic acid to the cobalt acetate is 1: 0.95, stirring for 15-20 minutes, standing, cooling to normal temperature, centrifugally separating out cobalt oxalate precipitate to obtain cobalt oxalate tetrahydrate, and further drying at 100 +/-5 ℃ to obtain cobalt oxalate dihydrate, wherein the product quality meets the requirement of analytical purity standard. The filtrate is recovered and returned to be used for preparing the raw material liquid for preparing the cobalt acetate.
Example 18
250kg of the same technical grade metallic cobalt as in example 16 were charged into a reactor having an effective volume of 80l and connected to a vacuum system at the outlet. Injecting the acetic acid peroxide, acetic acid and water into a reactor from a reactor feed inlet positioned at the upper part of a metal cobalt layer through a liquid distribution or diversion device, wherein the feeding speed is 1100kg/h, the concentration of the acetic acid peroxide is 5 percent, the concentration of the acetic acid is 8 percent, the reaction temperature is kept at 95 +/-5 ℃ by adjusting a heating and condensing device on the reactor, and the vacuum degree is adjusted to be (9.0 +/-0.2) multiplied by 104Pa, continuously discharging the generated cobalt acetate solution from the bottom of the reactor, filtering, and taking samples to determine that the product quality meets the standard requirements of GB1290-77 and HG/T2302-1999 in China, wherein the solution does not contain nitrate, chloride and 1/100 with the nickel content lower than the standard requirements, the production rate of the cobalt acetate is 1825g/l.h, and the utilization rate of the acetic peroxide is 81%.
The invention adopts symbols to explain that:
percent: mass percent; g: g; kg: kilogram; min: the method comprises the following steps of (1) taking minutes; h: hours; ml: ml; l: lifting; cm: centimeters; pa: and (6) handkerchief.
The cobalt acetate production rate of the present invention refers to the amount of cobalt acetate tetrahydrate per liter of active reactor per unit time that can be produced.
The utilization rate of the peroxyacetic acid or the hydrogen peroxide is as follows: the ratio of the theoretical consumption to the actual consumption of the peroxyacetic acid or hydrogen peroxide is calculated by a stoichiometric formula and is calculated by the following formula:
the stoichiometric formula of the chemical reaction involved in the invention is as follows:
(1)
(2)
(3)
in the equation brackets, S represents a solid; l represents a liquid.
The quality analysis method of the cobalt acetate adopts Chinese GB1290-77 and HG/T2302-1999 standards.
The quality standard of the cobalt oxalate in the invention is referred to the book of encyclopedia of chemical engineering, the first edition, the sixth volume, 111 page table 18, the chemical industry publishing house, Beijing, 1994 and 8 months. The method comprises the steps of measuring cobalt in the cobalt oxalate by a titration method, measuring metal impurities by an atomic absorption method, measuring chloride and sulfate by a colorimetric method and measuring alkali metals by a gravimetric method.
As can be seen from the above examples 1 to 18, the present invention has the following features compared with the prior art:
1. the invention promotes the liquid-solid reaction by adopting new technical characteristics, improves the utilization rate of hydrogen peroxide and the yield of cobalt acetate, and simultaneously provides a method for preparing cobalt acetate by directly and efficiently reacting the acetic peroxide with metal cobalt.
2. The invention further reduces the requirement on the specific surface area of the metal cobalt, and the cobalt raw material source is wider.
3. The invention gives consideration to the utilization rate and the production rate of raw materials and reduces the production cost.
4. The invention provides a method for preparing cobalt acetate and cobalt oxalate with high purity, and is convenient for industrial implementation.
5. The preparation method of the cobalt acetate and the cobalt oxalate provided by the invention has the advantages of simple process, low energy consumption and no environmental pollution.
Claims (4)
1. A method for preparing cobalt acetate, in a reactor with heating and condensing plant, add metal cobalt, peroxide acetic acid or hydrogen peroxide, acetic acid and water to mix, inject into reactor from locating at reactor feed inlet of upper portion of metal cobalt layer evenly, the cobalt acetate salt solution produced at the same time is discharged from the reactor bottom continuously; the method is characterized in that: the concentration of the peroxyacetic acid is 0.5-20% or the concentration of the hydrogen peroxide is 0.2-10%, the concentration of the acetic acid is 3-40%, the temperature is 50-140 ℃, and the pressure is 5.0 multiplied by 104Pa～4.0×105Pa。
2. The methodfor preparing cobalt acetate according to claim 1, wherein the metal cobalt used is technical grade metal cobalt without any ultra-fine dispersion treatment.
3. A method for preparing cobalt oxalate is characterized in that metallic cobalt, acetic acid peroxide or hydrogen peroxide, acetic acid and water are added into a reactor with a heating and condensing device and are uniformly injected into the reactor from a reactor feed inlet positioned at the upper part of a metallic cobalt layer after being mixed, and simultaneously, a generated cobalt acetate salt solution is continuously discharged from the bottom of the reactor, wherein in the preparation method of the cobalt acetate, the concentration of the acetic acid peroxide is 0.5-20% or the concentration of the hydrogen peroxide is 0.2-10%, the concentration of the acetic acid is 3-40%, the temperature is 50-140 ℃, and the pressure is 5.0 x 104Pa～4.0×105Pa, directly reacting the cobalt acetate salt solution with oxalic acid to obtain cobalt oxalate precipitate; the method is characterized in that: the mol ratio of the oxalic acid to the cobalt acetate is 1: 0.8-1.2.
4. The method for preparing cobalt oxalate according to claim 3, wherein oxalic acid is added directly to the cobalt acetate salt solution.
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| CN102584562A (en) * | 2011-12-23 | 2012-07-18 | 南京化学试剂有限公司 | Preparation method of cobalt acetate solution |
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