CN103951555A - Preparation method of dendrite-shaped nickel oxalate - Google Patents
Preparation method of dendrite-shaped nickel oxalate Download PDFInfo
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- CN103951555A CN103951555A CN201410179629.7A CN201410179629A CN103951555A CN 103951555 A CN103951555 A CN 103951555A CN 201410179629 A CN201410179629 A CN 201410179629A CN 103951555 A CN103951555 A CN 103951555A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Abstract
The invention provides a preparation method of dendrite-shaped nickel oxalate. The preparation method comprises the following processing steps: preparing a nickel chloride solution with nickel content of 120-180g/l for later use; constantly adding ammonia water into the nickel chloride solution until pH value of the solution is 8.0-9.0; controlling the solution temperature to be 60-70 DEG C, constantly dropwise adding an oxalic acid solution while stirring until that nickel content in supernatant fluid is less than or equal to 0.5g/L, filtering the solution left after reaction, washing precipitate, and drying the precipitate to obtain the dendrite-shaped nickel oxalate product. The preparation method provided by the invention can be used for preparing the dendrite-shaped nickel oxalate with good morphology, the controllability of crystal morphology is good, and the process is easy; as the dendrite-shaped nickel oxalate has special topography; after the dendrite-shaped nickel oxalate prepared by the preparation method is made into nickel powder, the nickel powder has special properties, and is widely applied to the battery industry, and the product price of the nickel powder is much higher than that of electrolytic reduction nickel powder.
Description
Technical field
The invention belongs to technical field of non-ferrous metallurgy, relate to a kind of preparation method of dendritic crystal state nickelous oxalate.
Background technology
Nickel oxide powder is because having multiple crystal habit and different shape characteristics, thereby under different condition, show different physicochemical properties, at aspects such as battery electrode, catalyzer, semi-conductor, magneticsubstance, glass and enamel, there is wide market application foreground, become gradually the new focus of nano materials research.And nickelous oxalate is exactly originally a kind of well behaved catalyzer raw materials on organic catalysis, especially along with the development of modern organic synthesis chemical technology, the no longer single use nickel of catalyzer, cobalt and precious metal, mostly seek many matrixes composite catalyst, to improve the usefulness of catalyzer, nickelous oxalate, as raw material, has just in time met needs prepared by composite catalyst.Prepare the powder-product that Special Nickel Powder and ultra-fine nickel oxide etc. have special property, substantially all rely on nickelous oxalate presoma and realize.Nickelous oxalate can be produced chemical nickel powder through thermolysis, reduction.Dendritic crystal state nickelous oxalate, because having special pattern, makes after nickel powder, has special character, is widely used in battery industry, and its price also exceeds 50,000 yuan ~ 60,000 yuan than electrolytic reduction nickel powder.Present stage, on market, also do not sell at present dendritic crystal state nickelous oxalate producer, what most of producer sold is all the common nickelous oxalate that does not require pattern.
From point of chemical reaction, can there is precipitin reaction in nickel salt solution and oxalate, oxalic nickel.Nickel salt solution is as single nickel salt, nickelous chloride and nickelous nitrate, is all that the simple and nickel ion of negatively charged ion matches outwardly, but sulfate radical, chlorine root, nitrate radical have very large impact to preparing the nickelous oxalate of different-shape.According to current research, showing, is in master's medium at sulfate radical, almost can not prepare different-shape nickelous oxalate; In Cl ~-Media, can realize the controlled of pattern; It would be desirable nitrate radical medium, but its reaction mechanism is not very clear and definite, this be also nickelous oxalate as the polytropy of presoma and the complicacy place of preparation process, and the cost of the production of nitric acid medium own is higher.
Summary of the invention
The object of the invention is to the problem existing for prior art, the preparation method of the good and simple dendritic crystal state nickelous oxalate of technique of a kind of crystal morphology controllability is provided.
For this reason, the present invention adopts following technical scheme:
A preparation method for dendritic crystal state nickelous oxalate, comprises following processing step:
The nickel chloride solution that configuration nickel content is 120-180g/l is stand-by; In nickel chloride solution, constantly add ammoniacal liquor, until pH is 8.0～9.0; Control solution temperature at 60 ℃～70 ℃, under agitation constantly drip oxalic acid solution, until nickel content≤0.5g/L in supernatant liquor, solution filter after reacting, and by washing of precipitate, will after drying precipitate, obtain dendritic crystal state nickelous oxalate product.
Further, described oxalic acid solution is saturated solution.
Reaction principle of the present invention is as follows:
The selection of a, raw material
The selection of nickelous chloride: show according to current research, can realize the morphology control of nickelous oxalate in Cl ~-Media, and nickelous chloride is more cheap compared to nickelous nitrate price.
The selection of oxalic acid: for avoiding bringing into other impurity, when preparing nickelous oxalate, should avoid selecting oxalate solution, oxalic acid solution can not be also saturated solution simultaneously, but for avoiding producing too much waste water, the present invention adopts saturated solution, and oxalic acid solution adds difficult too fast.
B. the control of temperature
Under same concentrations and pH condition, temperature of reaction has a great impact the pattern of nickelous oxalate and particle diameter.The nickelous oxalate making is at low temperatures agglomerated into platy shaped particle, and along with temperature raises, dendritic crystal state particle increases.When temperature is elevated to 65 ℃, generation be nearly all dendritic crystal state, and dispersed better; As temperature continues to raise, it is more and more thicker that dendritic crystal state can become.Reason is, crystallization medium temperature raises and makes the interfacial tension lowering between solid, liquid two-phase, and spread coefficient increases, can reduce nucleus growth speed and improve nucleus growth speed, thereby, be conducive to obtain large crystal; In addition, temperature raises, and the solubleness of solute increases makes balance move to the direction of dissolving, and is conducive to equally obtain large crystallization; When small crystal is when existing in solution compared with macrocrystal simultaneously, if solution is to being saturated compared with macrocrystal, to small-crystalline unsaturation, rising temperature, so small-crystalline first dissolves, then on macrocrystal surface, again separate out, promote crystal to grow up, so the optimal reaction temperature of preparing the nickelous oxalate of dendritic crystal state is 60 ℃～70 ℃.
The control of C, PH
Simple nickel chloride solution is slightly acidic, and when pH value of solution is less than 7.0 while being slightly acidic, gained particle is sharp-featured cuboid; The initial pH of solution is greater than 7.0 and is less than at 8.0 o'clock, and gained particle is all spherical in shape; The initial pH of solution is greater than at 8.0 o'clock, and particle is dendritic crystal state.In addition; pH value is too high; the nickelous oxalate crystal grain that initial stage forms can return molten; this is mainly relevant with the degree of supersaturation of solution; solution degree of supersaturation is little; solute exists mainly with the form of molecule or molecular clustering, particle grow up by these molecules (bunch) to nucleating surface diffusion, collect attached, grow up etc. and to realize.And when degree of supersaturation is large, can there is the homogeneous nucleation of explosive type in moment, form a large amount of small grains (particle diameter is from several nanometers to tens nanometers), this has just suppressed the diffusion type growth of secondary nucleation and particle, and the ionic strength in solution is high, greatly reduced the electrostatic double layer thickness of particle surface, the electrostatic repulsion conductively-closed between these small grains, makes the cohesion between small grains complete by quick agglomeration mechanism.Now, the intrinsic habit of crystal grain is by externalities---and high degree of supersaturation suppresses, and the random collision between small grains causes the speed of growth of each direction in space almost equal, the final spherical or spherical particle that forms axles such as leveling off to.Therefore ammonia nickel amount is higher than (pH value), and the nickel particles concentration that of dissociating is just less, and the degree of supersaturation of the nickelous oxalate that forms of being combined with oxalate denominationby is just lower, now, nickel oxalate is to grow under state non-being forced to, and can pull out himself crystal habit and reach full growth, and finally obtains elongated piece.When ammonia nickel amount is lower than (pH value), situation is just in time contrary, and particle is mainly grown up by Collision coagulation mode coalescence, and what obtain is spherical or particle that class is spherical.And pH value is too high; ammonia is excessive too many, and the oxalic acid adding for the first time, first neutralization reaction occurs; the consumption of oxalic acid is strengthened; simultaneous reactions speed is slow, easily forms little crystal grain, therefore; pH value is too high; the nickelous oxalate crystal grain that initial stage forms can return molten, and therefore, according to experiment, pH value is controlled at 8～9 o'clock and is advisable.
D. oxalic acid adds mode
In nickel ammonia complex solution, add oxalic acid liquid, the pattern of the nickelous oxalate particle of preparing presents near-spherical and two kinds of structures of dendritic crystal state with the pH difference of nickel ammonia complex solution.And with solid form, directly adding fashionablely when oxalic acid, oxalic acid particle is precipitation particles separates out the nucleation interface that provides possible, is conducive to the formation of spherical or spherical particle.Oxalic acid adds fashionable nickelous oxalate with dendritic crystal state structural generation with liquid form, therefore oxalic acid adds with liquid form.
E. ammoniacal liquor adds
With ammoniacal liquor nickelous chloride complexing or use liquefied ammonia complex ni-ion, solution during to certain pH value nickel ion completely by complexing, then drip oxalic acid solution, nickel ion is slowly discharged from nickel ammine matter, in this process, can remain that pH value is in certain scope simultaneously.Owing to there being a large amount of ammonia to exist in system, add pH in reaction process and remain on certain limit, cause the precipitin reaction speed of nickel and oxalic acid slower, have the regular hour to make crystal grain-growth, the crystal grain of nickelous oxalate is along certain direction growth, and then the nickelous oxalate of formation needle-like or dendritic crystal state.
To sum up, beneficial effect of the present invention is: can prepare the dendritic crystal state nickelous oxalate with good pattern, crystal morphology controllability is good and technique is simple; Because having special pattern, dendritic crystal state nickelous oxalate prepared by the present invention, after making nickel powder, has special character, is widely used in battery industry, and its product price also exceeds much than electrolytic reduction nickel powder.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph under the prepared dendritic crystal state nickelous oxalate of the present invention amplifies 200 times;
Fig. 2 is the scanning electron microscope (SEM) photograph under the prepared dendritic crystal state nickelous oxalate of the present invention amplifies 2000 times.
Embodiment
embodiment 1
A preparation method for dendritic crystal state nickelous oxalate, comprises following processing step:
The nickel chloride solution that configuration nickel content is 120g/l is stand-by; In nickel chloride solution, constantly add ammoniacal liquor, until pH is 8.5; Control solution temperature at 70 ℃, under agitation constantly drip oxalic acid solution, until nickel content≤0.5g/L in supernatant liquor, solution filter after reacting, and by washing of precipitate, will after drying precipitate, obtain dendritic crystal state nickelous oxalate product.
embodiment 2
A preparation method for dendritic crystal state nickelous oxalate, comprises following processing step:
The nickel chloride solution that configuration nickel content is 150g/l is stand-by; In nickel chloride solution, constantly add ammoniacal liquor, until pH is 9.0; Control solution temperature at 65 ℃, under agitation constantly drip oxalic acid solution, until nickel content≤0.5g/L in supernatant liquor, solution filter after reacting, and by washing of precipitate, will after drying precipitate, obtain dendritic crystal state nickelous oxalate product.
embodiment 3
A preparation method for dendritic crystal state nickelous oxalate, comprises following processing step:
The nickel chloride solution that configuration nickel content is 180g/l is stand-by; In nickel chloride solution, constantly add ammoniacal liquor, until pH is 8.0; Control solution temperature at 60 ℃, under agitation constantly drip oxalic acid solution, until nickel content≤0.5g/L in supernatant liquor, solution filter after reacting, and by washing of precipitate, will after drying precipitate, obtain dendritic crystal state nickelous oxalate product.
Claims (2)
1. a preparation method for dendritic crystal state nickelous oxalate, is characterized in that, comprises following processing step:
The nickel chloride solution that configuration nickel content is 120-180g/l is stand-by; In nickel chloride solution, constantly add ammoniacal liquor, until pH is 8.0～9.0; Control solution temperature at 60 ℃～70 ℃, under agitation constantly drip oxalic acid solution, until nickel content≤0.5g/L in supernatant liquor, solution filter after reacting, and by washing of precipitate, will after drying precipitate, obtain dendritic crystal state nickelous oxalate product.
2. the preparation method of a kind of dendritic crystal state nickelous oxalate according to claim 1, is characterized in that, described oxalic acid solution is saturated solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134235A (en) * | 2018-09-17 | 2019-01-04 | 郑州工程技术学院 | A kind of preparation method of the complicated oxalic acid nickel salt of threadiness |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651584A (en) * | 2005-02-06 | 2005-08-10 | 金川集团有限公司 | Production method of dentritic morphology nickel powder |
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- 2014-04-30 CN CN201410179629.7A patent/CN103951555A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651584A (en) * | 2005-02-06 | 2005-08-10 | 金川集团有限公司 | Production method of dentritic morphology nickel powder |
Non-Patent Citations (2)
| Title |
|---|
| TAKESHI OKAMATO，ET AL.: "Synthesis of Needle-like Nickel Powder by Thermal Decomposition of Nickel Oxalate", 《SHIGEN-TO-SOZAI》, vol. 121, no. 6, 24 February 2007 (2007-02-24), pages 255 - 259 * |
| 童长钿等: "超细草酸镍粒子的制备及其形状和粒度控制", 《湿法冶金》, vol. 22, no. 1, 31 March 2003 (2003-03-31), pages 22 - 26 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134235A (en) * | 2018-09-17 | 2019-01-04 | 郑州工程技术学院 | A kind of preparation method of the complicated oxalic acid nickel salt of threadiness |
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Inventor after: Yang Zhiqiang Inventor after: Zhang Guoyong Inventor after: Sun Zhengde Inventor after: Zhang Bing Inventor after: Li Baoping Inventor after: Xing Xiaozhong Inventor after: Chen Shengwei Inventor after: Shi Jinqiu Inventor after: Wang Yongzhu Inventor after: Ren Wei Inventor after: Tan Weimin Inventor after: Cao Zengcheng Inventor before: Yang Zhiqiang Inventor before: Zhang Guoyong Inventor before: Zhang Bing Inventor before: Li Baoping Inventor before: Xing Xiaozhong Inventor before: Chen Shengwei Inventor before: Shi Jinqiu Inventor before: Wang Yongzhu Inventor before: Ren Wei Inventor before: Tan Weimin Inventor before: Cao Zengcheng |
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Free format text: CORRECT: INVENTOR; FROM: YANG ZHIQIANG LI BAOPING XING XIAOZHONG CHEN SHENGWEI SHI JINQIU WANG YONGZHU REN WEI TAN WEIMIN CAO ZENGCHENG ZHANG GUOYONG ZHANG BING TO: YANG ZHIQIANG LI BAOPING XING XIAOZHONG CHEN SHENGWEI SHI JINQIU WANG YONGZHU REN WEI TAN WEIMIN CAO ZENGCHENG ZHANG GUOYONG SUN ZHENGDE ZHANG BING |
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Application publication date: 20140730 |