CN1101341C - Equipment for preparing spherical powder of nickelous hydroxide series - Google Patents
Equipment for preparing spherical powder of nickelous hydroxide series Download PDFInfo
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- CN1101341C CN1101341C CN98114412A CN98114412A CN1101341C CN 1101341 C CN1101341 C CN 1101341C CN 98114412 A CN98114412 A CN 98114412A CN 98114412 A CN98114412 A CN 98114412A CN 1101341 C CN1101341 C CN 1101341C
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Abstract
The present invention relates to equipment for preparing spherical powder of nickelous hydroxide series, which is characterized in that the equipment is composed of 2 to 4 orderly connected reaction kettles with stirrers; the reaction kettles have the basically same volumetric capacity and shape; the content liquid level with orderly graded distribution and the difference value of liquid level height between 20 to 500mm, wherein the first reaction kettle is provided with an overflow port, two charging ports with firm flow discharge, namely a quantitative feed port of a nickel salt solution, a quantitative feed port of a caustic solution, a quantitative feed port of an aqueous solution of ammonia and a finely adjusted charging port as a finely adjusted feed port of a caustic solution. The reaction kettles except for the first reaction kettle are additionally provided with a feed port; the overflow port of the previous reaction kettle is orderly connected with the feed port of the next reaction kettle so as to ensure that nickelous hydroxide and the suspension of other products in the previous reaction kettle are introduced into the next reaction kettle. The preparation equipment of the present invention has the advantages of stable reaction system, short required time and simple operating technology.
Description
The present invention relates to the technology of preparing of material, the producing apparatus of a kind of sphere or class spheroidal nickelous hydroxide series powder is provided especially.
The nickelous hydroxide series powder mainly is used as the positive electrode active materials of NI-G and nickel-hydrogen secondary cell and alkaline cell etc., general nickel hydroxide producing apparatus is at present: add caustic solution in a reaction vessel or in a plurality of independently reaction vessel and act on nickel salt aqueous solution generation precipitation, in reaction vessel, have stirring, obtain nickel hydroxide through operations such as solid-liquid separation, washing, dryings then.Because it is to carry out in a reactor or in a plurality of independently reaction vessel that nickel hydroxide generates, the nickel hydroxide Granularity Distribution that obtains like this is unreasonable, and tapped density is low, and its tamped density is low when making before the electrode materials furnishing pasty state.Perhaps, cause the tapped density instability of nickel hydroxide product owing in the reaction process of each reactor, constantly generate seed, thus unstable product quality.This be battery production producer do not wish the hydroxide nickel material that obtains.
The special equipment of opening flat 3-252318 communique record of day disclosure special permission, as shown in Figure 1.Nickel salt solution and caustic-alkali aqueous solution are imported in reactor 1, the reactor 2 simultaneously, the nickel salt solution in reactor 1 and the reactor 2 and the molar concentration rate of caustic-alkali aqueous solution are 1: 2, it also is 1: 2 that two reactor reaction solns add velocity ratio, the nickel hydroxide that generates in two reactors and the suspension liquid of other product overflow in the reactor 3 simultaneously, product with aforesaid reaction vessel 1 and 2 in reactor 3 carries out mechanical stirring, obtains nickel hydroxide continuously.In reaction process, be interrupted the generation seed crystal by being interrupted the pH value or the ammoniacal liquor add-on that change reactor 1 and 2.The nickel hydroxide product tapped density that this reaction system obtains can reach more than the 2.00g/ml.But there is following shortcoming in this reaction system: when being interrupted the generation seed crystal, the tapped density of its nickel hydroxide product is low, unstable product quality, can not satisfy the quantity-produced requirement, and because product is the product mechanical stirring by two kinds of particle size range, the nickel hydroxide product particle skewness of manufacturing.
The up-to-date open special permission spy of Japan drives the producing apparatus that flat 9-283135 has announced nickel hydroxide.This reaction unit has continuous crystallisation to separate out the synthetic groove of the reactor of nickel hydroxide and nickel ammine, adjust the feedway of nickel salt solution and additive metal salt solution with pure water, as shown in Figure 2.This reaction unit can will react with uniform mixing such as nickel salt solutions, but its reactor also only is a reactor, can not solve nickel hydroxide product tapped density problem of unstable.
The object of the present invention is to provide a kind of producing apparatus of spheroidal nickelous hydroxide series powder, it is short that the reaction system of this producing apparatus is stablized required time, operating procedure is simple, the nickelous hydroxide series powder size of being produced distributes rationally, thereby performance and tapped density are stable, as electrode active material and the mashed prod good fluidity of making after conductive agent mixes, tamped density height.
The invention provides a kind of producing apparatus of spheroidal nickelous hydroxide series powder, it is characterized in that: this equipment is linked in sequence by the reactor of 2～4 belt stirrers (7) and forms; Volume of each reactor (10) and shape basically identical, the content liquid level is docile and obedient the preface Gradient distribution, liquid level differs 20～500mm, wherein each reactor is provided with an overflow port (11), three base runoff charging openings, be that the quantitative inlet of nickel salt solution (1), the quantitative inlet of caustic solution (2), the quantitative inlet of ammonia soln (3) and a fine setting charging opening are caustic solution fine setting inlet (4); Other reactors except that first reactor increase an opening for feed (13), the overflow port of previous reactor (11) links to each other successively with the opening for feed (13) of a back reactor, makes the suspension liquid of nickel hydroxide in the previous reactor and other product enter a back reactor.
In addition, the aspect ratio of the internal diameter of reactor (10) and overflow port (11) is 1: 1.0～1.5 among the present invention.
The rotating speed of agitator among the present invention (7) is 300～1500 rev/mins.
Operating process of the present invention is such, whole process is to carry out in the successive reaction still under brute force stirs, be that the nickel hydroxide of previous reactor generation and the suspension liquid of other product overflow the back reactor of supply continuously, the supply flow rate of each reaction kettle for reaction thing solution is inconsistent, the reaction soln flow proportional of its each reactor and next reactor is that other reaction conditions control in 1: 0.5～0.8, three reactor is in full accord; Reactant is 1.5～2.2mol/l single nickel salt salts solution and contains 6.0～10.0mol/l caustic solution of nickel mole number 30～100% ammonia, and perhaps 1.5～2.2mol/l single nickel salt salts solution and concentration are 25～28% strong aqua and the caustic solution of 6.0～10.0mol/l; Reactant single nickel salt salts solution and alkali ammonia mixing solutions are pressed M
2+With OH
-Mol ratio 1: 2.5～3.0 or single nickel salt salts solution and alkaline solution and concentrated ammonia solution add by 1: 2.0～2.5: 0.3～1.0 molar ratio; Reactant mean residence time in reactor is selected between 5～15 hours; Temperature of reaction is a certain fixed value between 40～80 ℃ and be controlled at ± 2 ℃; The pH value of reaction solution is in 10.5～11.5 a certain fixed values, and the pH value amplitude that reaches control solution by the feed rate of adjusting alkaline solution or alkali ammonia mixing solutions is ± 0.1; Each still stirring intensity is 300～1500 rev/mins.In above-mentioned scope,, change the solid-to-liquid ratio of reaction solution by adjusting these parameters, thus the loose density of control nickelous hydroxide series powder, tapped density, granularity gradient etc.
Major advantage of the present invention is:
1) reaction conditions of the present invention is easy to control, can produce the nickelous hydroxide series sphere or the class spherical powder product of stable performance.Reaction system is stable only need 10 days left and right sides time.
2) the nickelous hydroxide series powder that the present invention produced is sphere or class sphere, and it is very convenient to wash, and its loose density and tap density height can reach 1.5～1.8g/ml, 2.00～2.3g/ml respectively.This powder before making electrode during the furnishing pasty state, good fluidity, tamped density height.
3) the nickelous hydroxide series product produced of working condition of the present invention is surmised to distribute and is easy to control, and its particle diameter scope is 2～50 μ m, and the average particulate diameter scope is 8～20 μ m.
Below by embodiment in detail the present invention is described in detail.
Accompanying drawing 1 is the special spheroidal nickelous hydroxide series powder producing apparatus synoptic diagram of opening flat 3-252318 communique record of day disclosure special permission.
Accompanying drawing 2 is opened the spheroidal nickelous hydroxide series powder producing apparatus synoptic diagram that flat 9-283135 announces for day disclosure special permission is special.
Accompanying drawing 3 is an equipment synoptic diagram provided by the invention.
Embodiment 1
As shown in Figure 3, the producing apparatus of spheroidal nickelous hydroxide series powder, being linked in sequence by the reactor of 3 belt stirrers (7) forms; Volume of each reactor (10) and shape basically identical are 1m
3Reactor diameter and aspect ratio are 1: 1.2, the content liquid level is docile and obedient the preface Gradient distribution, liquid level differs 20～500mm, wherein each reactor top, liquid level have an overflow port (11), three base runoff charging openings, promptly the quantitative inlet of nickel salt solution (1), the quantitative inlet of caustic solution (2), the quantitative inlet of ammonia soln (3) and a fine setting charging opening are the little inlet (4) of establishing of caustic solution; Other reactors except that first reactor increase an opening for feed (13), the overflow port of previous reactor (11) links to each other successively with the opening for feed (13) of a back reactor, makes the suspension liquid of nickel hydroxide in the previous reactor and other product enter a back reactor.Be inserted with pH meter (5) and thermometer (6) in each reactor, seal by reactor sealing cover (8).
The mixing salt of single nickel salt salts solution as single nickel salt volumetric molar concentration 2.0mol/l, rose vitriol volumetric molar concentration 0.4mol/l, zinc sulfate volumetric molar concentration 0.10mol/l used in reaction, the sodium hydroxide solution volumetric molar concentration is 6.0mol/l, 25～28% strong aquas, ammonia alkali volume ratio are 23: 100.The pH value of reaction system is controlled at 10.8 ± 0.1, and temperature of reaction is 50 ± 2 ℃.Stirring velocity is 1400rpm in the reaction, and the reaction solution mean residence time is 9 hours.Same reaction flow quantity additional proportion is 1: 0.8: 0.8 in first, second, third reactor.Reaction back nickelous hydroxide series particle is spherical, and loose density is 1.68g/ml, and tap density is 2.17g/ml, median size 16.3 μ m, particle diameter scope 2～40 μ m.
Embodiment 2
Difference from Example 1 is with two reactors, reaction uses the single nickel salt salts solution to be single nickel salt volumetric molar concentration 1.8mol/l, rose vitriol volumetric molar concentration 0.04mol/l, zinc sulfate volumetric molar concentration 0.08mol/l, the sodium hydroxide solution volumetric molar concentration is 6.0mol/l, and ammonia concn is 25～28%.The pH value of reaction system is controlled at 11.0 ± 0.1, and temperature of reaction is 55 ± 2 ℃.Stirring velocity is 1200rpm in the reaction, and the reaction solution mean residence time is 11 hours.Same reaction flow quantity additional proportion is 1: 0.7: 0.7 in first and second reactors.Reaction back nickelous hydroxide series particle is spherical, and loose density is 1.58g/ml, and tap density is 2.10g/ml, median size 14.2 μ m, particle diameter scope 2～30 μ m.
Claims (2)
1. the producing apparatus of a spheroidal nickelous hydroxide series powder is characterized in that: this equipment is linked in sequence by the reactor of 2～4 belt stirrers (7) and forms; Volume of each reactor (10) and shape basically identical, the content liquid level is docile and obedient the preface Gradient distribution, liquid level differs 20～500mm, wherein each reactor is provided with an overflow port (11), three base runoff charging openings, be that the quantitative inlet of nickel salt solution (1), the quantitative inlet of caustic solution (2), the quantitative inlet of ammonia soln (3) and a fine setting charging opening are caustic solution fine setting inlet (4); Other reactors except that first reactor increase an opening for feed (13), the overflow port of previous reactor (11) links to each other successively with the opening for feed (13) of a back reactor, makes the suspension liquid of nickel hydroxide in the previous reactor and other product enter a back reactor.
2. according to the producing apparatus of the described spheroidal nickelous hydroxide series powder of claim 1, it is characterized in that: the aspect ratio of the internal diameter of reactor (10) and overflow port (11) is 1: 1.0～1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114412A CN1101341C (en) | 1998-10-29 | 1998-10-29 | Equipment for preparing spherical powder of nickelous hydroxide series |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114412A CN1101341C (en) | 1998-10-29 | 1998-10-29 | Equipment for preparing spherical powder of nickelous hydroxide series |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1253118A CN1253118A (en) | 2000-05-17 |
| CN1101341C true CN1101341C (en) | 2003-02-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114412A Expired - Fee Related CN1101341C (en) | 1998-10-29 | 1998-10-29 | Equipment for preparing spherical powder of nickelous hydroxide series |
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| Country | Link |
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| CN (1) | CN1101341C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107986338B (en) * | 2017-11-23 | 2020-04-28 | 清远佳致新材料研究院有限公司 | Production device and process of nickel-cobalt-manganese ternary hydroxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0945104A (en) * | 1995-07-29 | 1997-02-14 | Fuakushisu Kk | Fuel lighting system |
| CN1193605A (en) * | 1997-03-14 | 1998-09-23 | 清华大学 | Preparation of high density and activity spherical nickle hydroxide |
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1998
- 1998-10-29 CN CN98114412A patent/CN1101341C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0945104A (en) * | 1995-07-29 | 1997-02-14 | Fuakushisu Kk | Fuel lighting system |
| CN1193605A (en) * | 1997-03-14 | 1998-09-23 | 清华大学 | Preparation of high density and activity spherical nickle hydroxide |
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| Publication number | Publication date |
|---|---|
| CN1253118A (en) | 2000-05-17 |
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