CN105692722B - A kind of method for reducing metal chloride spray pyrolysis and preparing chlorinity in oxide process - Google Patents

A kind of method for reducing metal chloride spray pyrolysis and preparing chlorinity in oxide process Download PDF

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CN105692722B
CN105692722B CN201610195086.7A CN201610195086A CN105692722B CN 105692722 B CN105692722 B CN 105692722B CN 201610195086 A CN201610195086 A CN 201610195086A CN 105692722 B CN105692722 B CN 105692722B
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temperature
powder
temperature control
powder collector
chlorinity
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CN105692722A (en
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王志兴
李滔
李新海
郭华军
李艳
彭文杰
胡启阳
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • 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
    • 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
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a kind of method for reducing metal chloride spray pyrolysis and preparing chlorinity in oxide process, comprise the following steps：Temperature control equipment is installed in powder collector；Pyrolysis Experiment will be carried out after metal chloride solutions ultrasonic atomizatio, the temperature in powder collector is controlled in a series of different temperature respectively by temperature control equipment, then thing phase or constituent analysis are carried out to the powder body material that is collected under different temperatures, selects not contain chlorine in powder material or temperature when chlorinity is less than 0.8wt% is as critical-temperature；Powder collector temperature control more than described critical-temperature, the production process that metal chloride spray pyrolysis prepares oxide is proceeded by.The method of the present invention can directly obtain high-purity mangesium oxide powder material, without follow-up individually dechlorination flow, so as to avoid the dechlorination such as washing, high temperature sintering, electrodialysis method to the negative effect caused by powder body material physicochemical properties.

Description

A kind of reduction metal chloride spray pyrolysis prepares chlorinity in oxide process Method
Technical field
The invention belongs to powder body material field, more particularly to a kind of metal chloride spray pyrolysis that reduces to prepare oxide mistake The method of chlorinity in journey.
Background technology
Transition metal oxide has extensive use in fields such as electrode material, catalyst, capacitor materials.With application The continuous expansion of scope, requirement to material performance itself also more and more higher.Therefore the primary rank that powder body material must be prepared Duan Jinhang is strictly controlled, and how to prepare high-purity, pattern rule, the metal oxide materials of function admirable becomes people pass The focus of note.Spray pyrolysis because with process is simple, raw efficiency high, prepared by that product component is uniform, purity is high etc. is many excellent Point is widely used in the preparation of various metal-oxide powder materials.Wherein, using the metal chloride aqueous solution as raw material, using spray Mist pyrolysismethod prepares NiO, Co3O4Deng powder body material when, easy residual chlorine element in product.The source of chlorine element be on the one hand by Not thorough in chloride decomposition, another aspect product is also to cause product by HCl (g) chlorinations in tail gas at powder collector A high key factor of chlorinity.With NiO, Co3O4Exemplified by, the reaction occurred at powder collector is respectively：
NiO+2HCl (g)=NiCl2+H2O(g)；
2Co3O4+ 12HCl (g)=6CoCl2+6H2O(g)+O2(g)。
When product is cooled to normality in powder collector, above-mentioned reaction is a thermodynamics spontaneous process.Residual chlorine can be right The combination property of metal oxide materials has a negative impact.Therefore, research reduces chlorinity in powder product, is prepared to follow-up Premium quality product and expand its application field important in inhibiting.
At present, it is general that it is removed using the method individually post-processed to reduce the negative effect of chlorion in all kinds of powders Chlorine purifies, and such as hydrogen reducing dechlorination, washing dechlorination, high temperature sintering dechlorination, electroosmose process trap to chlorion, although it Dechlorination effect it is fine, still, be required to numerous and diverse operating process, expensive equipment investment and consumption be certain is processed into This, while processing procedure can also impact to powder body material physicochemical properties.Thus, research one kind can be in metal chloride The method that spray pyrolysis prepares control chlorinity in oxide process is necessary.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided one Kind reduces the method that metal chloride spray pyrolysis prepares chlorinity in oxide process, passes through transition metal prepared by the method Oxide powder material chlorinity is low, and this method operating process is simple, and consuming cost is low, efficiency high, and will not be to material Material physicochemical properties impact.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of method for reducing metal chloride spray pyrolysis and preparing chlorinity in oxide process, comprises the following steps：
(1) temperature control equipment is installed in powder collector, by temperature control equipment so as to realizing powder collector In temperature reach controllable；
(2) Pyrolysis Experiment will be carried out after metal chloride solutions ultrasonic atomizatio, is collected powder by temperature control equipment Temperature in device controls in a series of different temperature respectively, then carries out thing phase to the powder body material being collected under different temperatures Or constituent analysis, select not contain chlorine in powder material or temperature when chlorinity is less than 0.8Wt% is as critical-temperature；When this When occurring not chloride or chlorinity in the powder material obtained in series of temperatures at multigroup temperature and being less than 0.8Wt%, selection temperature It is critical-temperature to spend one group of minimum temperature；
(3) powder collector temperature control more than the critical-temperature of gained, is proceeded by metal chlorination in step (2) Thing spray pyrolysis prepares the production process of oxide.Namely by controlling temperature by the reaction controlling in powder collector in oxygen The Chemistry and Physics Institute is in thermodynamic advantages region, so as to suppress powder body material by the chlorination of tail gas institute, so as to which reduction is prepared in oxide material Chlorinity.
Above-mentioned method, it is preferred that the metal chloride is at least one of nickel chloride, cobalt chloride, manganese chloride.
Above-mentioned method, it is preferred that in the step (2), the temperature model in temperature control equipment control powder collector Enclose for 150~450 DEG C.
Above-mentioned method, it is preferred that in the step (2), concentration of metal ions scope is in metal chloride solutions 0.25~1.5mol/L.
Above-mentioned method, it is preferred that in the step (2), pyrolysis temperature is 500~900 DEG C.
Above-mentioned method, it is preferred that in the step (2), thing phase or constituent analysis are to the chloride in powder body material Or chlorinity is tested and analyzed.
Compared with prior art, the advantage of the invention is that：
The present invention in tail gas and powder body material by the temperature control in powder collector by occurring the critical of chlorination reaction More than temperature, so as to suppress powder body material by the chlorination of tail gas institute, so as to reduce chlorinity in material.Thus the method for the present invention can To directly obtain high-purity mangesium oxide powder material, without follow-up individually dechlorination flow, so as to avoid washing, high temperature sintering, Electrodialysis etc. dechlorinates method to the negative effect caused by powder body material physicochemical properties.Method operation letter i.e. of the invention Single, consuming cost is low, efficiency high, small on the influence of material physical chemistry property, industrially with great application value.
Brief description of the drawings
Fig. 1 is the XRD spectrum of powder body material collected by powder collector under different temperatures in the embodiment of the present invention 1.
Fig. 2 is the EDS of powder body material collected by powder collector at 350 DEG C in 1 specific production process of the embodiment of the present invention Test collection of illustrative plates.
Fig. 3 is the EDS test collection of illustrative plates of powder body material collected by powder collector at 150 DEG C in the embodiment of the present invention 2.
Fig. 4 is the EDS test collection of illustrative plates of powder body material collected by powder collector at 400 DEG C in the embodiment of the present invention 2.
Fig. 5 is the EDS of powder body material collected by powder collector at 400 DEG C in 2 specific production process of the embodiment of the present invention Test collection of illustrative plates.
Fig. 6 is the XRD spectrum of powder body material collected by powder collector under different temperatures in the embodiment of the present invention 3.
Fig. 7 is the EDS tests of powder body material collected by powder collector at 350 DEG C during the embodiment of the present invention 3 specifically produces Collection of illustrative plates.
Embodiment
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment to invent herein do it is more complete Face, meticulously describe, but protection scope of the present invention is not limited to specific embodiment.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention's Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of reduction NiCl of the invention2The method that solution spray pyrolysis prepares chlorinity during NiO, including following step Suddenly：
(1) first equipment is improved, a temperature control equipment is installed in powder collector, made in powder collector Temperature realize it is controllable；
(2) first compound concentration is 0.5mol/L NiCl2Pyrolysis Experiment (spray pyrolysis temperature is carried out after solution ultrasonic atomizatio For 800 DEG C, carrier gas (O2) flow velocity is 6L/min), then by powder collector temperature control respectively 100 DEG C, 300 DEG C, 315 DEG C, 330 DEG C, 360 DEG C, the powder body material under different temperatures is collected, and by the powder XRD material phase analysis under different temperatures, test result As shown in Figure 1.As shown in Figure 1, when powder collector temperature is less than 300 DEG C, there is the diffraction maximum of nickel chloride in XRD spectrum, Showing product NiO, there occurs chlorination reaction with tail gas；When powder collector temperature is higher than 315 DEG C (300 DEG C and 360 DEG C), XRD Do not occur the diffraction maximum of nickel chloride in collection of illustrative plates, show that NiO and tail gas do not have that chlorination reaction occurs substantially；
(3) powder collector temperature control at 350 DEG C, the production process of system row high purity N iO powders is started.To institute Obtain product and carry out EDS tests, EDS test results are as shown in Fig. 2 as shown in Figure 2, the content of chlorine is only 0.22Wt% in product.
Embodiment 2：
A kind of reduction CoCl of the invention2Solution spray pyrolysis prepares Co3O4During chlorinity method, it is including following Step：
(1) first equipment is improved, a temperature control equipment is installed in powder collector, made in powder collector Temperature realize it is controllable；
(2) compound concentration is 0.5mol/L CoCl2Pyrolysis Experiment is carried out after solution ultrasonic atomizatio, and (spray pyrolysis temperature is 800 DEG C, carrier gas (O2) flow velocity is 6L/min), then powder collector temperature is controlled in 150 DEG C and 400 DEG C respectively, collect different At a temperature of powder body material, then by the powder collected under different temperatures carry out EDS tests.EDS test results such as Fig. 3, Fig. 4 institutes Show.From the figure 3, it may be seen that when powder collector temperature is 150 DEG C, the content of chlorine is 2.5Wt% in powder body material, shows product Co3O4There occurs chlorination reaction with tail gas；As shown in Figure 4, when powder collector temperature is 400 DEG C, chlorine contains in powder body material Measure as 0.79Wt%, show product Co3O4It is significantly suppressed with the direct chlorination reaction of tail gas；
(3) powder collector temperature control is proceeded by high-purity C o at 400 DEG C3O4The production process of powder.To institute Obtain product and carry out EDS tests, EDS test results are as shown in figure 5, as shown in Figure 5, the content of chlorine is 0.58Wt% in product.
Embodiment 3：
Chlorine contains during a kind of reduction nickel cobalt manganese mixed solution spraying pyrolysis of the invention prepares more composite oxide of metal The method of amount, comprises the following steps：
(1) first equipment is improved, a temperature control equipment is installed in powder collector, made in powder collector Temperature realize it is controllable；
(2) the nickel cobalt manganese mixed solution (Ni that total concentration of metal ions is 0.5mol/L is prepared:Co:Mn mol ratio is 8: 1:1) Pyrolysis Experiment is carried out after ultrasonic atomizatio, and (spray pyrolysis temperature is 800 DEG C, carrier gas (O2) flow velocity is 6L/min), then by powder Collector temperature is controlled as 200 DEG C, 300 DEG C, the powder under different temperatures is then collected, then to the powder under different temperatures Powder body material obtained in body collector carries out XRD material phase analysis, and XRD test results are as shown in fig. 6, it will be appreciated from fig. 6 that work as powder When body collector temperature is 200 DEG C, there is the diffraction maximum of nickel chloride in XRD spectrum, show more composite oxide of metal and tail gas There occurs chlorination reaction；When powder collector temperature is 300 DEG C, does not occur the diffraction maximum of chloride in XRD spectrum, show more Composite oxide of metal does not have that chlorination reaction occurs substantially with tail gas；
(3) powder collector temperature control at 350 DEG C, the life of the more composite oxide of metal powders of high-purity is proceeded by Production process.EDS tests are carried out to products obtained therefrom, EDS test results are as shown in fig. 7, as shown in Figure 7, the content of chlorine is in product 0.27Wt%.

Claims (6)

  1. A kind of 1. method for reducing nickel chloride spray pyrolysis and preparing chlorinity during NiO, it is characterised in that including following step Suddenly：
    (1) temperature control equipment is installed in powder collector；Temperature range in temperature control equipment control powder collector For 150~450 DEG C；
    (2) Pyrolysis Experiment will be carried out after nickel chloride solution ultrasonic atomizatio, by temperature control equipment by the temperature in powder collector Degree controls in a series of different temperature respectively, then carries out thing phase or composition point to the powder body material being collected under different temperatures Analysis, 315 DEG C of temperature when selecting not containing chlorine in powder material are used as critical-temperature；
    (3) powder collector temperature control is proceeded by nickel chloride spray pyrolysis at more than 315 DEG C of the middle gained of step (2) Prepare NiO production process.
  2. 2. the method as described in claim 1, it is characterised in that in step (2), the ion concentration range of nickel chloride solution is 0.25~1.5mol/L.
  3. 3. a kind of nickel cobalt manganese mixed chloride solution spray pyrolysis that reduces prepares chlorinity during more composite oxide of metal Method, it is characterised in that comprise the following steps：
    (1) temperature control equipment is installed in powder collector；Temperature range in temperature control equipment control powder collector For 150~450 DEG C；The metal chloride is nickel chloride, cobalt chloride, the mixture of manganese chloride；
    (2) Pyrolysis Experiment will be carried out after metal chloride solutions ultrasonic atomizatio, by temperature control equipment by powder collector Temperature control respectively in a series of different temperature, then the powder body material being collected under different temperatures is carried out thing phase or into Analysis, 300 DEG C of temperature when selecting not containing chlorine in powder material are used as critical-temperature；
    (3) it is mixed chlorinated to be proceeded by nickel cobalt manganese at more than 300 DEG C of the middle gained of step (2) for powder collector temperature control Thing spray pyrolysis prepares more composite oxide of metal production processes.
  4. 4. method as claimed in claim 3, it is characterised in that in the step (2), metal ion in metal chloride solutions Concentration range is 0.25~1.5mol/L.
  5. 5. the method as described in claim 1 or 3, it is characterised in that in the step (2), pyrolysis temperature is 500~900 DEG C.
  6. 6. the method as described in claim 1 or 3, it is characterised in that in the step (2), thing phase or constituent analysis are to powder Chloride or chlorinity in body material are tested and analyzed.
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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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CN103556152B (en) * 2013-11-11 2015-08-05 浙江科菲科技股份有限公司 A kind of mixed chlorinated copper spent etching solution synthetical recovery treatment process
CN104016598A (en) * 2014-06-20 2014-09-03 攀钢集团攀枝花钢铁研究院有限公司 Dechlorination method of titanium extraction tailings
CN105271857A (en) * 2015-11-17 2016-01-27 攀钢集团攀枝花钢铁研究院有限公司 Online dechlorination technology of chlorination process tailing slag extracted titanium

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