CN101130490A - Method for preparing cobaltous acetate solution - Google Patents
Method for preparing cobaltous acetate solution Download PDFInfo
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- CN101130490A CN101130490A CNA2007101308289A CN200710130828A CN101130490A CN 101130490 A CN101130490 A CN 101130490A CN A2007101308289 A CNA2007101308289 A CN A2007101308289A CN 200710130828 A CN200710130828 A CN 200710130828A CN 101130490 A CN101130490 A CN 101130490A
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Abstract
The invention discloses a making method of cobalt acetate solution, which comprises the following steps: placing metal cobalt powder, acetic acid solution with density at 0-30%(m/m) and concentrated nitric acid solution with density at 96-98%(m/m) in the reactor; stirring to reflux for 6-12 h under 90-100 deg. c; obtaining the cobalt acetate solution; setting the quality rate of acetic acid solution and concentrated nitric acid solution at 50: 0. 5-2. 5; making cobalt powder excessive. The invention simplifies the technical flow path under normal pressure without polluting to improve the product quality and reduce the impurity content and energy consumption and save raw material with low investment, which makes the cobalt content in the reacting liquid at 10%(m/m) in comparison with hydrogen peroxide solution method.
Description
Technical field
The present invention relates to the preparation method of the Preparation of Catalyst of field of fine chemical, particularly cobalt acetate solution.
Background technology
Cobaltous diacetate, manganese acetate are used for PTA (pure terephthalic acid) production equipment in a large number as oxide catalyst.The preparation method of Cobaltous diacetate has experienced continuous improvement.The method for preparing Cobaltous diacetate commonly used now is also referred to as " single stage method ".The step of " single stage method " preparation Cobaltous diacetate is: excessive cobalt is joined in the dilute acetic acid, the nitric acid that adds 3～4% (m/m) again, be heated to more than 100 ℃, successive reaction under reflux state needs approximately that cobalt contents reaches about 10% (m/m) stopped reaction in the 70h reaction solution, and then reacting by heating liquid, wherein excessive acetic acid is removed in evaporation, through operations such as deironing filtrations, makes Cobaltous diacetate at last again.In addition, also have electrolytic process, be about to cobalt metal and be electrolyzed to produce cobaltous hydroxide, through washing again with dilute acetic acid prepared in reaction Cobaltous diacetate.Belgium Umicore Company adopts high pressure liquid oxygen oxidation style, charges into liquid oxygen and cobalt metal prepared in reaction Cobaltous diacetate in acetum.The kind literary composition of China Jinan glass Cao of institute etc. adopts hydrogen peroxide as oxygenant, adds in the dilute acetic acid and cobalt metal prepared in reaction Cobaltous diacetate.Each favourable covering of above method.Preparation method commonly used adopts the reguline metal cobalt, and the abnormal reaction of reguline metal cobalt and non-oxidizing acid is slow, when these sour cobalt salts of preparation, needs to add a large amount of oxygenants.The oxygenant of usually full usefulness is nitric acid, hydrogen peroxide.Hydrogen peroxide can fast decomposition in reaction, keep then suitable difficulty of the stability of reacting.Nitric acid then can make the oxynitride of residual various valence states in a large number in the reaction solution as a large amount of uses of oxygenant and be difficult to remove, influence the quality of reaction solution, thereby reaction solution can not directly be used for preparing liquid catalyst, also brings difficulty for the recycling of the mother liquor after the crystallization simultaneously.
For growing PTA industry, original adoption Cobaltous diacetate and manganese acetate dissolution of crystals, preparation are adjusted to CoMn binary liquid state and import production equipment again and use, and be present then requirement is directly used in the CoMn binary liquid catalyst of PTA production equipment.PTA industry is more and more higher to the requirement of catalyzer, thereby, Preparation of catalysts technology and quality level are had higher requirement.
Each PTA production technique differs to the cobalt manganese content requirement in the cobalt manganese liquid catalyst, and usually cobalt contents is at 2%, 4%, 6% (m/m), manganese content 2%, 4%, 6% (m/m) scope, to the requirement of each impurity generally in ppm (m/m) level.In the preparation of cobalt manganese liquid catalyst, particularly crucial is the preparation of cobalt acetate solution, and wherein cobalt contents should be able to satisfy the requirement of 3%～9% (m/m).
Below with the preparation method of above-mentioned cobalt acetate solution, compare according to the requirement of PTA industry.
| The preparation method | Advantage | Shortcoming | Can reaction solution be directly used in the preparation liquid catalyst |
| Single stage method | Traditional technology | Speed of response is slow, long flow path; Impurity elimination process complexity; Efficient is low; Pollute big; The energy consumption height; Iron level is difficult to control in the product, and nitrate content is too high. | Can not.Need preparation finished product body product ability composite. |
| Electrolytic process | Can continuous production | Washing process is long; The energy consumption height; Yield poorly and just can obtain Cobaltous diacetate through two-step reaction | Can not.Must be behind thorough washing, two-step reaction could be composite. |
| The liquid oxygen method | The energy continuous production; Pollute less or the high reaction solution quality better of pollution-free yield | Invest high high top pressure operation tool insecurity | Can |
| The dioxygen water law | The energy continuous production; Less investment pollute less or pollution-free energy consumption low; The reaction solution quality better | Cobalt contents is low in the reaction solution, only can prepare cobalt contents at 2% cobalt manganese liquid catalyst, if must be higher than 2.5% cobalt manganese liquid catalyst or crystal Cobaltous diacetate by the preparation cobalt contents, needs to consume a large amount of heat energy and concentrates | Of course, but since reaction solution in cobalt contents low, its application is restricted. |
Summary of the invention
For solving the problem that above-mentioned technology exists, the present invention proposes and a kind ofly improve speed of reaction, reduce the method for preparing cobalt acetate solution of oxygenant consumption as far as possible.
Because the abnormal reaction of reguline metal cobalt and non-oxidizing acid is slow, when these sour cobalt salts of preparation, need to add a large amount of oxygenants.The oxygenant of usually full usefulness is nitric acid, hydrogen peroxide.Hydrogen peroxide can fast decomposition in reaction, keep then suitable difficulty of the stability of reacting.Nitric acid then can make the oxynitride of residual various valence states in a large number in the reaction solution as a large amount of uses of oxygenant and be difficult to remove, influence the quality of reaction solution, thereby reaction solution can not directly be used for preparing liquid catalyst, also brings difficulty for the recycling of the mother liquor after the crystallization simultaneously.
At above-mentioned situation, the present invention adopts following technical scheme:
With metal cobalt powder, concentration is that 20～30% (m/m) acetums and concentration are that the concentrated nitric acid solution of 96～98% (m/m) places reactor, 90～100 ℃ of following stirring and refluxing reactions, can make cobalt acetate solution in 6～12 hours; The mass ratio of aforementioned acetum and concentrated nitric acid solution is 50: 0.5～2.5, and cobalt powder is then for apparent excessively.The concentration of aforementioned acid is mass concentration.
Above-mentioned metal cobalt powder particle diameter should be preferably 100 orders less than 80 orders; The stirring velocity of reactor is 200～300 rev/mins during reaction; Be the transmission of reaction medium in the accelerating reactor, the present invention adopts propeller agitator.It is 8～10% (m/m) that the cobalt acetate solution that gets after the reaction contains the cobalt amount.
For holding back reaction evaporable acetic acid steam, in reaction process, institute's discharge tail gas is adopted the condensation of appropriateness, the control condensate temperature is about 85 ℃.
The present invention adopts metal cobalt powder, its particle diameter is less than 80 orders, and prior art adopts the cobalt metal piece usually, its piece directly is generally 25 * 20 * 8mm, both compare, its surface-area of the metal cobalt powder of homogenous quantities has increased at least 200 times, therefore corresponding being greatly improved of speed of reaction of metal cobalt powder and acid among the present invention, under the effect of low levels nitric acid oxidation agent, react with dilute acetic acid, can generate high-quality cobalt contents is the cobalt acetate solution of 8～10% (m/m), can directly prepare the CoMn liquid catalyst that satisfies the various cobalt contents demands of PTA manufacturer, also can be used for preparing the Acetic Acid Glacil cobalt.
Technical process of the present invention is simple, and synthesis under normal pressure is pollution-free, the product quality height, and foreign matter content is low, and energy consumption is low, and raw material consumption is few, invests not high.Compare with the dioxygen water law, the cobalt contents of reaction solution can be up to 10% in this patent, and the reaction solution cobalt contents that the dioxygen water law is produced has only 2～3% (m/m); Compare with single stage method, the entire reaction time shortens greatly, reacts required oxidant content and significantly reduces NO in the reaction solution
3 -Content is less than 100ppm (m/m), in traditional single stage method, and the NO in the reaction solution
3 -Content is generally up to 500～2000ppm (m/m).And principle of the present invention also can be used for preparing the cobalt salt of other non-oxidizing acid.
Embodiment
Embodiment 1
In the 500mL four-hole bottle of electric mixer, thermometer, spherical condensation tube is housed, add 257g22% (m/m) dilute acetic acid, the 30g cobalt powder, 3.78g66% (m/m) nitric acid, on electric mantle, heat back flow reaction, sampling analysis, cobalt contents is 8.57% (m/m) stopped reaction in complexometry analytical reaction liquid, lasts 6h.NO in the reaction solution
3 -＜100ppm (m/m), iron 2ppm (m/m), filtering afterreaction liquid quality is 276.0g, is weighed as 6.21g after the remaining cobalt powder washing drying, the cobalt yield is 99.4%.
Embodiment 2
In the 500mL four-hole bottle of electric mixer, thermometer, spherical condensation tube is housed, add 259g 28% (m/m) dilute acetic acid, the 30g cobalt powder, 3.50g66% (m/m) nitric acid, heat on electric mantle, back flow reaction is taken a sample behind the 6h, use the complexometry analysis, cobalt contents is 7.43% (m/m) in the reaction solution.7.5h the back sampling is 8.48% (m/m) with cobalt contents in the complexometry analytical reaction liquid, NO
3＜100ppm (m/m), iron 2ppm (m/m).Filtering afterreaction liquid quality is 270.3g, is weighed as 6.89g after the remaining cobalt powder washing drying, and the cobalt yield is 99.1%.
Embodiment 3
In the 500mL four-hole bottle of electric mixer, thermometer, spherical condensation tube is housed, add 258g 25% (m/m) dilute acetic acid, the 30g cobalt powder, 1.40g66% (m/m) nitric acid, heat on electric mantle, back flow reaction is taken a sample behind the 7.5h, use the complexometry analysis, cobalt contents is 7.52% in the reaction solution.9.0h the back sampling is 8.35% (m/m) with cobalt contents in the complexometry analytical reaction liquid, NO
3 -＜100ppm (m/m), iron 2ppm (m/m).Filtering afterreaction liquid quality is 264.5g, is weighed as 7.65g after the remaining cobalt powder washing drying, and the cobalt yield is 98.8%.
Embodiment 4
In the 500mL four-hole bottle of electric mixer, thermometer, spherical condensation tube is housed, add 258g 25% (m/m) dilute acetic acid, the 30g cobalt powder, 4.90g66% (m/m) nitric acid, heat on electric mantle, back flow reaction is taken a sample behind the 5.0h, use the complexometry analysis, cobalt contents is 7.74% (m/m) in the reaction solution.8.0h the back sampling is 9.85% (m/m) with cobalt contents in the complexometry analytical reaction liquid, NO
3 -＜100ppm (m/m), iron 2ppm (m/m).Filtering afterreaction liquid quality is to be weighed as 2.57g after the remaining cobalt powder washing drying of 276.0g, and the cobalt yield is 99.1%.
The industrial application example:
Propeller agitator, thermometer, 4m are being housed
2In the 1000L reactor of shell and tube prolong, add 516.3kg 25% (m/m) dilute acetic acid, the 60kg cobalt powder, 10kg66% (m/m) nitric acid, heating, back flow reaction is taken a sample behind the 7h, uses the complexometry analysis, and cobalt contents is 8.28% (m/m) in the reaction solution.Reaction solution is analyzed after filtering, and the reaction solution total mass is 552.0kg.Cobalt contents 8.28% (m/m), free acetic acid 8% (m/m), NO
3 -＜100ppm (m/m), iron 2ppm (m/m), nickel 2.2ppm (m/m), copper 1.3ppm (m/m), zinc 0.5ppm (m/m).Be weighed as 13.84kg after the unreacted metal cobalt powder washing drying, the cobalt yield is 99.0%.
When beginning reaction need be heated to reflux temperature, when refluxing beginning after, under the situation that reaction heat constantly produces, need only insulation reaction can proceed.
Claims (6)
1. the preparation method of a cobalt acetate solution, it is characterized in that with metal cobalt powder, concentration being that 20～30% acetums and concentration are that 96～98% concentrated nitric acid solution places reactor 90～100 ℃ of following stirring and refluxing reactions, can make cobalt acetate solution in 6～12 hours; The mass ratio of aforementioned acetum and concentrated nitric acid solution is 50: 0.5～2.5, and cobalt powder then is excessive.
2. the preparation method of cobalt acetate solution as claimed in claim 1 is characterized in that described metal cobalt powder is that particle diameter is less than 80 orders.
3. the preparation method of cobalt acetate solution as claimed in claim 1, the stirring velocity of reaction is 200～300 rev/mins when it is characterized in that reacting.
4. the preparation method of cobalt acetate solution as claimed in claim 1 is characterized in that described agitator is a propeller agitator.
5. the preparation method of cobalt acetate solution as claimed in claim 1, the cobalt amount that contains that it is characterized in that reacting the cobalt acetate solution of back gained is 8～10% (m/m).
6. the preparation method of cobalt acetate solution as claimed in claim 1 is characterized in that institute's discharge tail gas being adopted the condensation of appropriateness in reaction process for holding back reaction evaporable acetic acid steam, and the control condensate temperature is about 85 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101308289A CN101130490A (en) | 2007-08-21 | 2007-08-21 | Method for preparing cobaltous acetate solution |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101308289A CN101130490A (en) | 2007-08-21 | 2007-08-21 | Method for preparing cobaltous acetate solution |
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| CN101130490A true CN101130490A (en) | 2008-02-27 |
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| CNA2007101308289A Pending CN101130490A (en) | 2007-08-21 | 2007-08-21 | Method for preparing cobaltous acetate solution |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584562A (en) * | 2011-12-23 | 2012-07-18 | 南京化学试剂有限公司 | Preparation method of cobalt acetate solution |
| US11855281B2 (en) * | 2018-05-26 | 2023-12-26 | Ge Solartech, LLC | Methods for the production of cathode materials for lithium ion batteries |
-
2007
- 2007-08-21 CN CNA2007101308289A patent/CN101130490A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584562A (en) * | 2011-12-23 | 2012-07-18 | 南京化学试剂有限公司 | Preparation method of cobalt acetate solution |
| US11855281B2 (en) * | 2018-05-26 | 2023-12-26 | Ge Solartech, LLC | Methods for the production of cathode materials for lithium ion batteries |
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