CN105692722A - Method for lowering chlorine content in oxide preparation process by metal chloride spray pyrolysis - Google Patents
Method for lowering chlorine content in oxide preparation process by metal chloride spray pyrolysis Download PDFInfo
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- CN105692722A CN105692722A CN201610195086.7A CN201610195086A CN105692722A CN 105692722 A CN105692722 A CN 105692722A CN 201610195086 A CN201610195086 A CN 201610195086A CN 105692722 A CN105692722 A CN 105692722A
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- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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Abstract
The invention discloses a method for lowering chlorine content in an oxide preparation process by metal chloride spray pyrolysis. The method comprises the following steps: installing a temperature controller in a powder collector, carrying out ultrasonic atomization on a metal chloride solution, carrying out a pyrolysis experiment, respectively controlling the temperature in the powder collector at a series of different temperatures by using the temperature controller, carrying out phase or composition analysis on the powder materials collected at different temperatures, and selecting the temperature, at which the chlorine content in the powder material is 0 or lower than 0.8 wt%, as the critical temperature; and controlling the temperature of the powder collector at the critical temperature or above, and carrying out the oxide preparation process by metal chloride spray pyrolysis. The method can directly obtain the high-purity oxide powder material without any subsequent independent dechlorination process, thereby avoiding the negative effects of water washing, high-temperature ignition, electrodialysis and other dechlorination methods on the physicochemical properties of the powder material.
Description
Technical field
The invention belongs to powder body material field, particularly relate to a kind of metal chloride spray pyrolysis that reduces and prepare the method for chlorinity in oxide process。
Background technology
Transition metal oxide is widely applied in fields such as electrode material, catalyst, capacitor materials。Along with the continuous expansion of range of application, the requirement of the performance of material own is also more and more higher。Therefore the primary stage must be prepared by powder body material strictly controls, how to prepare high-purity, pattern rule, function admirable metal oxide materials become people pay close attention to focus。Spray pyrolysis is widely used in the preparation of various metal-oxide powder material because having the plurality of advantages such as operation is simple, the rate that comes into force height, prepared product component is uniform, purity is high。Wherein, with metal chloride aqueous solution for raw material, spray pyrolysis is adopted to prepare NiO, Co3O4During Deng powder body material, easy residual chlorine element in product。The source of chlorine element is that product is also the key factor causing product chlorinity high by HCl (g) chlorination in tail gas at powder collector place on the other hand owing to chloride decomposes not thorough on the one hand。With NiO, Co3O4For example, the reaction occurred at powder collector place is respectively as follows:
NiO+2HCl (g)=NiCl2+H2O (g)；
2Co3O4+ 12HCl (g)=6CoCl2+6H2O(g)+O2(g)。
When in powder collector, product is cooled to normality, above-mentioned reaction is a thermodynamics spontaneous process。The combination property of metal oxide materials can be had a negative impact by residual chlorine。Therefore, research reduces chlorinity in powder body product, to follow-up preparation premium quality product and expand its application important in inhibiting。
At present, for reducing the negative effect of chloride ion in all kinds of powder body, it is generally adopted the way of independent post processing to its purification that dechlorinates, as chloride ion is carried out trapping etc. by hydrogen reducing dechlorination, washing dechlorination, high temperature sintering dechlorination, electroosmose process, although their dechlorination effect is fine, but, all need numerous and diverse operating process, expensive equipment investment and consume certain processing cost, powder body material physicochemical properties also can be impacted by processing procedure simultaneously。Thus, study that a kind of to prepare, at metal chloride spray pyrolysis, the method controlling chlorinity in oxide process be necessary。
Summary of the invention
The technical problem to be solved is, overcome the deficiency and defect mentioned in background above technology, a kind of metal chloride spray pyrolysis that reduces is provided to prepare the method for chlorinity in oxide process, the transition metal oxide powder body material chlorinity prepared by the method is low, and the method operating process is simple, consuming cost is low, and efficiency is high, and will not material physical chemistry character be impacted。
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is:
A kind of metal chloride spray pyrolysis that reduces prepares the method for chlorinity in oxide process, comprises the following steps:
(1) temperature control equipment is installed in powder collector, by temperature control equipment thus the temperature realized in powder collector reaches controlled；
(2) Pyrolysis Experiment is carried out by after metal chloride solutions ultrasonic atomizatio, by temperature control equipment, the temperature in powder collector is controlled in a series of different temperature respectively, then the powder body material collected under different temperatures is carried out thing phase or component analysis, selects temperature when not containing chlorine or chlorinity lower than 0.8Wt% in powder material as critical temperature；When all occurring in the powder material obtained at group temperature many in this series of temperatures that not chloride or chlorinity is lower than 0.8Wt%, the one group of temperature selecting temperature minimum is critical temperature；
(3) powder collector temperature is controlled more than the critical temperature of gained, to proceed by metal chloride spray pyrolysis and prepare the production process of oxide in step (2)。Namely by controlling temperature by the reaction controlling in powder collector in thermodynamic advantages region, oxide place, thus suppressing powder body material by the chlorination of tail gas institute, thus the chlorinity in oxide material is prepared in reduction。
Above-mentioned method, it is preferred that described metal chloride is at least one in Nickel dichloride., cobaltous chloride, manganese chloride。
Above-mentioned method, it is preferred that in described step (2), the temperature range that temperature control equipment controls in powder collector is 150～450 DEG C。
Above-mentioned method, it is preferred that in described step (2), in metal chloride solutions, concentration of metal ions ranges for 0.25～1.5mol/L。
Above-mentioned method, it is preferred that in described step (2), pyrolysis temperature is 500～900 DEG C。
Above-mentioned method, it is preferred that in described step (2), thing phase or component analysis are the chloride in powder body material or chlorinity carry out detection analyze。
Compared with prior art, it is an advantage of the current invention that:
The present invention by controlling more than the critical temperature of tail gas and powder body material generation chlorination reaction by the temperature in powder collector, thus suppressing powder body material by the chlorination of tail gas institute, thus reducing chlorinity in material。Thus the method for the present invention can directly obtain high-purity mangesium oxide powder material, it is not necessary to follow-up independent dechlorination flow process, thus avoiding the negative effect that powder body material physicochemical properties are caused by the dechlorination methods such as washing, high temperature sintering, electrodialysis。Namely the method for the present invention is simple to operate, and consuming cost is low, and efficiency is high, and material physical chemistry characteristics influence is little, industrially has great using value。
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of powder body material collected by powder collector under different temperatures in the embodiment of the present invention 1。
The EDS that Fig. 2 is powder body material collected by powder collector at 350 DEG C in the concrete production process of the embodiment of the present invention 1 tests collection of illustrative plates。
The EDS that Fig. 3 is powder body material collected by powder collector at 150 DEG C in the embodiment of the present invention 2 tests collection of illustrative plates。
The EDS that Fig. 4 is powder body material collected by powder collector at 400 DEG C in the embodiment of the present invention 2 tests collection of illustrative plates。
The EDS that Fig. 5 is powder body material collected by powder collector at 400 DEG C in the concrete production process of the embodiment of the present invention 2 tests collection of illustrative plates。
Fig. 6 is the XRD figure spectrum of powder body material collected by powder collector under different temperatures in the embodiment of the present invention 3。
The EDS that Fig. 7 is powder body material collected by powder collector at 350 DEG C during the embodiment of the present invention 3 specifically produces tests collection of illustrative plates。
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, invention herein is done more comprehensively, described meticulously, but protection scope of the present invention is not limited to specific embodiment。
Unless otherwise defined, to be generally understood that implication with those skilled in the art identical in all technical term used hereinafter。Technical term used herein is intended merely to the purpose describing specific embodiment, is not intended to limit the scope of the invention。
Unless otherwise specified, the various raw materials used in the present invention, reagent, instrument and equipment etc. all can be commercially available by market or can be prepared by existing method。
Embodiment 1:
A kind of reduction NiCl of the present invention2The method of chlorinity in NiO process is prepared in solution spray pyrolysis, comprises the following steps:
(1) first equipment is improved, powder collector is installed a temperature control equipment, makes the temperature in powder collector realize controlled；
(2) first compound concentration is the NiCl of 0.5mol/L2(spray pyrolysis temperature is 800 DEG C, carrier gas (O to carry out Pyrolysis Experiment after solution ultrasonic atomizatio2) flow velocity is 6L/min), then powder collector temperature is controlled respectively at 100 DEG C, 300 DEG C, 315 DEG C, 330 DEG C, 360 DEG C, collect the powder body material under different temperatures, and by the powder body XRD material phase analysis under different temperatures, test result is as shown in Figure 1。As shown in Figure 1, when powder collector temperature is lower than 300 DEG C, XRD figure spectrum occurs the diffraction maximum of Nickel dichloride., it was shown that product NiO and tail gas there occurs chlorination reaction；When powder collector temperature is higher than 315 DEG C (300 DEG C and 360 DEG C), XRD figure spectrum does not occur the diffraction maximum of Nickel dichloride., it was shown that NiO and tail gas are substantially free of generation chlorination reaction；
(3) powder collector temperature is controlled at 350 DEG C, start the production process of system row high purity N iO powder body。Products obtained therefrom carries out EDS test, as in figure 2 it is shown, as shown in Figure 2, in product, the content of chlorine is only 0.22Wt% to EDS test result。
Embodiment 2:
A kind of reduction CoCl of the present invention2Co is prepared in solution spray pyrolysis3O4The method of chlorinity in process, comprises the following steps:
(1) first equipment is improved, powder collector is installed a temperature control equipment, makes the temperature in powder collector realize controlled；
(2) compound concentration is the CoCl of 0.5mol/L2(spray pyrolysis temperature is 800 DEG C, carrier gas (O to carry out Pyrolysis Experiment after solution ultrasonic atomizatio2) flow velocity is 6L/min), then powder collector temperature is controlled respectively at 150 DEG C and 400 DEG C, collect the powder body material under different temperatures, then the powder body collected under different temperatures is carried out EDS test。EDS test result is such as shown in Fig. 3, Fig. 4。From the figure 3, it may be seen that when powder collector temperature is 150 DEG C, in powder body material, the content of chlorine is 2.5Wt%, it was shown that product Co3O4Chlorination reaction is there occurs with tail gas；As shown in Figure 4, when powder collector temperature is 400 DEG C, in powder body material, the content of chlorine is 0.79Wt%, it was shown that product Co3O4It is significantly suppressed with the direct chlorination reaction of tail gas；
(3) powder collector temperature is controlled, at 400 DEG C, to proceed by high-purity C o3O4The production process of powder body。Products obtained therefrom carries out EDS test, as it is shown in figure 5, as shown in Figure 5, in product, the content of chlorine is 0.58Wt% to EDS test result。
Embodiment 3:
The method of chlorinity in many composite oxide of metal process is prepared in the reduction nickel cobalt manganese mixed solution spraying pyrolysis of a kind of present invention, comprises the following steps:
(1) first equipment is improved, powder collector is installed a temperature control equipment, makes the temperature in powder collector realize controlled；
(2) (spray pyrolysis temperature is 800 DEG C, carrier gas (O to carry out Pyrolysis Experiment after preparing nickel cobalt manganese mixed solution (mol ratio of Ni:Co:Mn the is 8:1:1) ultrasonic atomizatio that total concentration of metal ions is 0.5mol/L2) flow velocity is 6L/min), again powder collector temperature is controlled as 200 DEG C, 300 DEG C, then the powder body under different temperatures is collected, then the powder body material obtained in the powder collector under different temperatures is carried out XRD material phase analysis, XRD test result as shown in Figure 6, it will be appreciated from fig. 6 that when powder collector temperature is 200 DEG C, XRD figure spectrum occurs the diffraction maximum of Nickel dichloride., it was shown that many composite oxide of metal and tail gas there occurs chlorination reaction；When powder collector temperature is 300 DEG C, there is not muriatic diffraction maximum in XRD figure spectrum, it was shown that many composite oxide of metal and tail gas are substantially free of generation chlorination reaction；
(3) powder collector temperature is controlled, at 350 DEG C, to proceed by the production process of high-purity many composite oxide of metal powder body。Products obtained therefrom carries out EDS test, as it is shown in fig. 7, as shown in Figure 7, in product, the content of chlorine is 0.27Wt% to EDS test result。
Claims (6)
1. one kind is reduced metal chloride spray pyrolysis and prepares the method for chlorinity in oxide process, it is characterised in that comprise the following steps:
(1) temperature control equipment is installed in powder collector；
(2) Pyrolysis Experiment is carried out by after metal chloride solutions ultrasonic atomizatio, by temperature control equipment, the temperature in powder collector is controlled in a series of different temperature respectively, then the powder body material collected under different temperatures is carried out thing phase or component analysis, selects temperature when not containing chlorine or chlorinity lower than 0.8wt% in powder material as critical temperature；
(3) powder collector temperature is controlled more than the critical temperature of gained, to proceed by metal chloride spray pyrolysis and prepare the production process of oxide in step (2)。
2. the method for claim 1, it is characterised in that described metal chloride is at least one in Nickel dichloride., cobaltous chloride, manganese chloride。
3. the method for claim 1, it is characterised in that in described step (2), the temperature range that temperature control equipment controls in powder collector is 150～450 DEG C。
4. the method for claim 1, it is characterised in that in described step (2), in metal chloride solutions, concentration of metal ions ranges for 0.25～1.5mol/L。
5. the method for claim 1, it is characterised in that in described step (2), pyrolysis temperature is 500～900 DEG C。
6. the method for claim 1, it is characterised in that in described step (2), thing phase or component analysis are the chloride in powder body material or chlorinity carry out detection analyze。
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Cited By (5)
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| CN106784780A (en) * | 2017-03-03 | 2017-05-31 | 中南大学 | A kind of nickel-based oxide presoma and its preparation method and application |
| CN107601547A (en) * | 2017-08-28 | 2018-01-19 | 中南大学 | The control method of remaining chlorinity in metal oxide |
| CN108178197A (en) * | 2017-12-14 | 2018-06-19 | 金川集团股份有限公司 | A kind of preparation method of electron level nickel protoxide |
| CN108706640A (en) * | 2018-07-13 | 2018-10-26 | 金川集团股份有限公司 | A kind of preparation method of nickel oxide powder material |
| CN112551601A (en) * | 2019-09-26 | 2021-03-26 | 荆门市格林美新材料有限公司 | Spray pyrolysis preparation method and device of nickel oxide powder |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106784780A (en) * | 2017-03-03 | 2017-05-31 | 中南大学 | A kind of nickel-based oxide presoma and its preparation method and application |
| CN107601547A (en) * | 2017-08-28 | 2018-01-19 | 中南大学 | The control method of remaining chlorinity in metal oxide |
| CN108178197A (en) * | 2017-12-14 | 2018-06-19 | 金川集团股份有限公司 | A kind of preparation method of electron level nickel protoxide |
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| CN112551601A (en) * | 2019-09-26 | 2021-03-26 | 荆门市格林美新材料有限公司 | Spray pyrolysis preparation method and device of nickel oxide powder |
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