CN102381958A - Ammonia circulative preparation method for cobaltous oxalate - Google Patents
Ammonia circulative preparation method for cobaltous oxalate Download PDFInfo
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- CN102381958A CN102381958A CN2011102838861A CN201110283886A CN102381958A CN 102381958 A CN102381958 A CN 102381958A CN 2011102838861 A CN2011102838861 A CN 2011102838861A CN 201110283886 A CN201110283886 A CN 201110283886A CN 102381958 A CN102381958 A CN 102381958A
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Abstract
The invention relates to an ammonia circulative preparation method for cobaltous oxalate. In the current commonest liquid phase precipitation method, because ammonium salt is introduced in the reaction process and the amount of oxalic acid is excessive during the reaction, impurities like ammonia nitrogen and oxalic acid root in synthesized waste water are required for processing. According to the invention, cobalt liquid is taken as a raw material, an oxalic acid solution is used for absorbing ammonia gas to prepare an ammonium oxalate solution which can be taken as an auxiliary material, cobalt liquid and the ammonium oxalate solution are added in a reaction vessel for synthesizing to obtain cobaltous oxalate pulp, the cobaltous oxalate pulp is filtered and washed, and dried to obtain the cobaltous oxalate product; simultaneously, waste water after filtering and washing is carried out pH regulation, ammonia molecule is separated from waste water by using an air stripping method, the oxalic acid solution is absorbed to be the ammonium oxalate solution for realizing the ammonia circulative utilization. The preparation method of the invention has the advantages that ammonia circulative utilization is realized, the waste water treatment avoids the introduction of ammonium salt and ammonia nitrogen, the production cost is reduced and the circular economy is realized.
Description
Technical field
The present invention relates to the preparation of sour cobalt, particularly a kind of method of ammonia cycles prepare cobalt oxalate.
Background technology
Cobalt oxalate is usually as the important source material of producing cobalt powder and oxide compound thereof, and latest developments show that cobalt oxalate also is used as the functional materials of excellent performance in many other fields and obtains using widely gradually.For example, lithium cell field part producer adopts just progressively to promote and adopts cobalt oxalate powder as the negative pole raw material now, and in catalyst field, cobalt oxalate powder also just is applied, and develops cobalt oxalate powder in addition and prepares technology of electromagnet material or the like.
The preparation method of cobalt oxalate powder mainly contains solid reaction process, solid-liquid phase reaction method and liquid phase reaction method etc.Solid reaction process adopts the solid of cobalt salt and oxalate as raw material, through grinding, with solid state reaction mode synthesis of oxalic acid cobalt; Its shortcoming is: also must introduce large amount of organic in the solid state reaction process, and solid state reaction takes place at the interface of two solid phases, homogeneity is relatively poor, and at room temperature speed of response is too slow, and economic benefit is relatively poor.Solid-liquid phase reaction method (like patent documentation CN101780545A) adopts cobaltous carbonate powder and oxalic acid solution prepared in reaction cobalt oxalate, but this method needs preparation cobaltous carbonate powder earlier, and operation is longer, and cost is high.Liquid-phase precipitation method is present the most general method, and it adopts solubility cobalt salt and ammonium oxalate to be mixed with liquid stock usually, adopts liquid-liquid hybrid mode to react then, have that technology is simple, reaction soon and low cost and other advantages; But because reaction process introduced ammonium salt, and oxalic acid is excessive during reaction, contains impurity such as ammonia nitrogen and oxalate in the waste water after synthetic and needs processing.For the processing of this waste water, part producer adopts electrodialysis and evaporative crystallization method to handle, and this method energy consumption is high, and cost is high, and the maintenance of the equipment difficulty is big.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency that above-mentioned prior art exists, and proposes a kind of method of ammonia cycles prepare cobalt oxalate, to avoid introducing the wastewater treatment of new ammonium salt and ammonia nitrogen, reduces production costs, and realizes recycling economy.
In order to achieve the above object, the technical scheme that the present invention adopts is following: the method for ammonia cycles prepare cobalt oxalate, and its step is following:
(a). adopt pure water that cobalt salt is dissolved as cobalt liquid, cobalt liquid can be a kind of in NSC 51149, rose vitriol, the cobalt nitrate solution; The 5-30% that in cobalt liquid, presses the cobalt quality adds one or more in ammoniacal liquor, EDTA, the ammonium citrate, forms the complex cobalt salts solution;
(b). adopt pure water that oxalic acid is dissolved as oxalic acid solution, absorbing ammonia with oxalic acid solution becomes ammonium oxalate solution;
(c). with the ammonium oxalate solution of complex cobalt salts solution and excessive 5-25%, add reaction kettle, control synthetic temperature of reaction is 30-70 ℃, and pH value in reaction is 2.0-3.0, and stirring velocity is 400-1000rpm, makes the cobalt oxalate ore pulp continuously with complexing-homogeneous precipitation method;
(d). the cobalt oxalate ore pulp filters, washs, and the wet cobalt oxalate that obtains carries out drying, gets the cobalt oxalate finished product;
(e). the waste water that filter, washing produces, add pH regulator agent such as quicklime or calcium hydroxide and regulate pH to 6-7, make excessive oxalate generate caoxalate, settlement separate solid wherein;
(f). with above-mentioned supernatant after settlement separate; Further adopt the pH regulator agent to regulate pH to 10-13; Adopting blow-off method is ammonia with ammonium root stripping wherein; Ammonia adopts oxalic acid solution to absorb becomes ammonium oxalate solution, if the complexing agent that preparation complex cobalt salts solution adopts is an ammoniacal liquor, the part ammonia that then stripping is produced absorbs with cobalt liquid and becomes complex cobalt salts solution (being cobalt ammonium complex solution); Clear liquid behind the stripping effluxes.
The present invention is a raw material with cobalt liquid, adopts ammonium oxalate solution that oxalic acid solution absorbs the ammonia preparation as auxiliary material, cobalt liquid and ammonium oxalate solution is joined to synthesize in the reaction kettle obtain the cobalt oxalate ore pulp, it is carried out filtration washing, and drying obtains the cobalt oxalate finished product; Simultaneously, the waste water of filtration washing is regulated pH, and adopt blow-off method, amino molecule is separated from waste water, adopt oxalic acid solution to be absorbed as ammonium oxalate solution, realize the recycle of ammonia.
Compare with existing method, the present invention has the following advantages:
1. the cobalt oxalate powder morphology, the controllable granularity that adopt complex-precipitation method of the present invention to make;
2. adopt blow-off method stripping ammonium root to become amino molecule, realized the recycle of ammonia, avoided the discharging difficult problem of ammonia nitrogen;
3. adopt oxalic acid solution directly to absorb ammonia, avoided ammonia to be dissolved as ammoniacal liquor, saved operation;
4. the present invention has realized the recycle of ammonia, has avoided introducing the wastewater treatment of new ammonium salt and ammonia nitrogen, helps reducing production costs, and has realized recycling economy.
Below in conjunction with Figure of description and embodiment the present invention is described further.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the embodiment of the invention 1 a cobalt oxalate shape appearance figure.
Fig. 3 is the embodiment of the invention 2 cobalt oxalate shape appearance figures.
Fig. 4 is the embodiment of the invention 3 cobalt oxalate shape appearance figures.
Embodiment
Embodiment 1
As shown in Figure 1, adopt the dissolving of chlorination cobalt salt, obtain 30-90g/L cobalt liquid, wherein one or more of 5%-30% adding ammoniacal liquor, EDTA, ammonium citrate of in above-mentioned cobalt liquid, press the cobalt quality are as the complex cobalt salts solution.With the oxalic acid dissolving, obtain the 50-100g/L oxalic acid solution, absorb ammonia and obtain ammonium oxalate solution.With excessive 5%-25% ammonium oxalate solution and complex cobalt salts solution; Use and stream or the reinforced method adding of drag flow reaction kettle; Control synthetic temperature of reaction is 30 ℃-70 ℃; PH value in reaction is 2.0-3.0, and stirring velocity is 400 rpm-1000rpm, makes the cobalt oxalate ore pulp continuously with complexing-homogeneous precipitation method; The cobalt oxalate ore pulp is after band filter filters, washs, and wet cobalt oxalate carries out drying, obtains the cobalt oxalate finished product, and pine is than being 0.23g/cm
3, Fisher particle size is 1.21 μ m, pattern is bar-shaped (its pattern is as shown in Figure 2).Simultaneously, the waste water that filter, washing produces adds quicklime or calcium hydroxide and regulates pH to 6-7, makes excessive oxalate generate caoxalate, settlement separate solid wherein.With the supernatant after settlement separate; Further add calcium hydroxide or sodium hydroxide and regulate pH to 10-13; Adopting blow-off method is ammonia with ammonium root stripping wherein; Ammonia adopts oxalic acid solution to absorb becomes ammonium oxalate solution, if preparation complex cobalt salts solution complexing agent adopts ammoniacal liquor, then the part ammonia of stripping generation is absorbed by cobalt liquid becomes the complex cobalt salts solution.Clear liquid behind the stripping can efflux.
Embodiment 2
As shown in Figure 2, adopt the dissolving of sulfuric acid cobalt salt, obtain 30-90g/L cobalt liquid, wherein one or more of 10%-30% adding ammoniacal liquor, EDTA, ammonium citrate of in above-mentioned cobalt liquid, press the cobalt quality are as the complex cobalt salts solution.With the oxalic acid dissolving, obtain the 50-100g/L oxalic acid solution, absorb ammonia and obtain ammonium oxalate solution.With excessive 5%-25% ammonium oxalate solution and complex cobalt salts solution; Use and stream or the reinforced method adding of drag flow reaction kettle; Control synthetic temperature of reaction is 30 ℃-70 ℃; PH value in reaction is 2.0-3.0, and stirring velocity is 400 rpm-1000rpm, makes the cobalt oxalate ore pulp continuously with complexing-homogeneous precipitation method; The cobalt oxalate ore pulp is after band filter filters, washs, and wet cobalt oxalate carries out drying, obtains the cobalt oxalate finished product, and pine is than being 0.18g/cm
3, Fisher particle size is 0.95 μ m, pattern is bar-shaped (its pattern is as shown in Figure 3).Simultaneously, the waste water that filter, washing produces adds quicklime or calcium hydroxide and regulates pH to 6-7, makes excessive oxalate generate caoxalate, settlement separate solid wherein.With the supernatant after settlement separate; Further add calcium hydroxide or sodium hydroxide and regulate pH to 10-13; Adopting blow-off method is ammonia with ammonium root stripping wherein; Ammonia adopts oxalic acid solution to absorb becomes ammonium oxalate solution, if preparation complex cobalt salts solution complexing agent adopts ammoniacal liquor, then the part ammonia of stripping generation is absorbed by cobalt liquid becomes the complex cobalt salts solution.Clear liquid behind the stripping can efflux.
Embodiment 3
As shown in Figure 1, adopt the dissolving of nitric acid cobalt salt, obtain 30-90g/L cobalt liquid, wherein one or more of the 10%-25% adding ammoniacal liquor, EDTA, ammonium citrate of in above-mentioned cobalt liquid, press the cobalt quality are as the complex cobalt salts solution.With the oxalic acid dissolving, obtain the 60-100g/L oxalic acid solution, absorb ammonia and obtain ammonium oxalate solution.With excessive 10%-20% ammonium oxalate solution and complex cobalt salts solution; Use and stream or the reinforced method adding of drag flow reaction kettle; Control synthetic temperature of reaction is 30 ℃-70 ℃; PH value in reaction is 2.0-3.0, and stirring velocity is 500 rpm-1000rpm, makes the cobalt oxalate ore pulp continuously with complexing-homogeneous precipitation method; The cobalt oxalate ore pulp is after band filter filters, washs, and wet cobalt oxalate carries out drying, obtains the cobalt oxalate finished product, and pine is than being 0.3g/cm
3, Fisher particle size is 1.2 μ m, pattern type of being spherical (its pattern is as shown in Figure 4).Simultaneously, the waste water that filter, washing produces adds quicklime or calcium hydroxide and regulates pH to 6-7, makes excessive oxalate generate caoxalate, settlement separate solid wherein.With the supernatant after settlement separate; Further add calcium hydroxide or sodium hydroxide and regulate pH to 10-13; Adopting blow-off method is ammonia with ammonium root stripping wherein; Ammonia adopts oxalic acid solution to absorb becomes ammonium oxalate solution, if preparation complex cobalt salts solution complexing agent adopts ammoniacal liquor, then the part ammonia of stripping generation is absorbed by cobalt liquid becomes the complex cobalt salts solution.Clear liquid behind the stripping can efflux.
Claims (4)
1. the method for ammonia cycles prepare cobalt oxalate, its step is following:
A). adopt pure water that cobalt salt is dissolved as cobalt liquid, the 5-30% that in cobalt liquid, presses the cobalt quality adds complexing agent, forms the complex cobalt salts solution;
B). adopt pure water that oxalic acid is dissolved as oxalic acid solution, absorbing ammonia with oxalic acid solution becomes ammonium oxalate solution;
C). with the ammonium oxalate solution of complex cobalt salts solution and excessive 5-25%, add reaction kettle, control synthetic temperature of reaction is 30-70 ℃, and pH value in reaction is 2.0-3.0, and stirring velocity is 400-1000rpm, makes the cobalt oxalate ore pulp continuously with complexing-homogeneous precipitation method;
D). the cobalt oxalate ore pulp filters, washs, and the wet cobalt oxalate that obtains carries out drying, gets the cobalt oxalate finished product;
E). the waste water that filter, washing produces, add the pH regulator agent and regulate pH to 6-7, make excessive oxalate generate caoxalate, settlement separate solid wherein;
F). with above-mentioned supernatant after settlement separate; Further adopt the pH regulator agent to regulate pH to 10-13; Adopting blow-off method is ammonia with ammonium root stripping wherein; Ammonia adopts oxalic acid solution to absorb becomes ammonium oxalate solution, if the complexing agent that preparation complex cobalt salts solution adopts is an ammoniacal liquor, the part ammonia that then stripping is produced absorbs with cobalt liquid and becomes the complex cobalt salts solution; Clear liquid behind the stripping effluxes.
2. the method for ammonia cycles prepare cobalt oxalate according to claim 1 is characterized in that described cobalt liquid is any in NSC 51149, rose vitriol, the cobalt nitrate solution.
3. the method for ammonia cycles prepare cobalt oxalate according to claim 1 is characterized in that described complexing agent is the mixture of any or several kinds in ammoniacal liquor, EDTA, the ammonium citrate.
4. the method for ammonia cycles prepare cobalt oxalate according to claim 1 is characterized in that described pH regulator agent is quicklime or calcium hydroxide.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478699A (en) * | 2014-12-10 | 2015-04-01 | 广东光华科技股份有限公司 | Preparation method of high-purity superfine cobalt oxalate powder |
| CN104478700A (en) * | 2014-12-09 | 2015-04-01 | 英德佳纳金属科技有限公司 | Large-particle size cobalt oxalate and preparation method thereof |
| CN105742626A (en) * | 2014-12-09 | 2016-07-06 | 荆门市格林美新材料有限公司 | Ni-Co composite oxide and preparation method thereof |
| CN107759464A (en) * | 2017-10-26 | 2018-03-06 | 北京科技大学 | A kind of single dispersing oxalic acid copper powders controllable method for preparing |
| CN110511133A (en) * | 2019-09-06 | 2019-11-29 | 辽宁星空钠电电池有限公司 | A kind of method that rapid precipitation prepares one-dimensional cobalt oxalate |
| CN107840793B (en) * | 2017-10-26 | 2021-04-20 | 北京科技大学 | Preparation method of special-shaped monodisperse zinc oxalate powder |
| CN113416129A (en) * | 2021-06-21 | 2021-09-21 | 温州大学新材料与产业技术研究院 | Preparation method and application of spherical cobalt oxalate |
| CN113909485A (en) * | 2021-10-11 | 2022-01-11 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478700A (en) * | 2014-12-09 | 2015-04-01 | 英德佳纳金属科技有限公司 | Large-particle size cobalt oxalate and preparation method thereof |
| CN105742626A (en) * | 2014-12-09 | 2016-07-06 | 荆门市格林美新材料有限公司 | Ni-Co composite oxide and preparation method thereof |
| CN104478699A (en) * | 2014-12-10 | 2015-04-01 | 广东光华科技股份有限公司 | Preparation method of high-purity superfine cobalt oxalate powder |
| CN107759464A (en) * | 2017-10-26 | 2018-03-06 | 北京科技大学 | A kind of single dispersing oxalic acid copper powders controllable method for preparing |
| CN107759464B (en) * | 2017-10-26 | 2020-11-17 | 北京科技大学 | Controllable preparation method of monodisperse copper oxalate powder |
| CN107840793B (en) * | 2017-10-26 | 2021-04-20 | 北京科技大学 | Preparation method of special-shaped monodisperse zinc oxalate powder |
| CN110511133A (en) * | 2019-09-06 | 2019-11-29 | 辽宁星空钠电电池有限公司 | A kind of method that rapid precipitation prepares one-dimensional cobalt oxalate |
| CN110511133B (en) * | 2019-09-06 | 2022-04-12 | 辽宁星空钠电电池有限公司 | Method for preparing one-dimensional cobalt oxalate through rapid precipitation |
| CN113416129A (en) * | 2021-06-21 | 2021-09-21 | 温州大学新材料与产业技术研究院 | Preparation method and application of spherical cobalt oxalate |
| CN113416129B (en) * | 2021-06-21 | 2022-07-19 | 温州大学新材料与产业技术研究院 | Preparation method and application of spherical cobalt oxalate |
| CN113909485A (en) * | 2021-10-11 | 2022-01-11 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
| CN113909485B (en) * | 2021-10-11 | 2023-11-17 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
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Application publication date: 20120321 |