CN101497432B - Method for preparing single or composite metal oxide by atomizing and oxidizing solution - Google Patents
Method for preparing single or composite metal oxide by atomizing and oxidizing solution Download PDFInfo
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- CN101497432B CN101497432B CN2009100428530A CN200910042853A CN101497432B CN 101497432 B CN101497432 B CN 101497432B CN 2009100428530 A CN2009100428530 A CN 2009100428530A CN 200910042853 A CN200910042853 A CN 200910042853A CN 101497432 B CN101497432 B CN 101497432B
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Abstract
The invention discloses a method for preparing single or composite metal oxide by solution atomization oxidation and special devices thereof. The method comprises the following steps: preparing a 0.1-3 mol/L single or composite soluble metal salt solution, adding a macromolecular dispersant according to 0.1 to 1 weight percent of metals in the solution into the solution, and preheating the solution to between 60 and 80 DEG C; inputting the solution into an airflow type atomizer of the special devices for solution atomization oxidation, atomizing the solution under the condition that the atomization pressure is between 1.0 and 2.5*10<5> Pa, allowing the solution to enter a vertical tubular electric furnace through a disturbing flow device of the special devices, fully mixing the solution and the air at a temperature of between 500 and 950 DEG C, and instantaneously oxidizing the mixture into oxide powder; and allowing the oxide powder to enter a high-efficiency cyclone separator for separation, and allowing sour gas in a vapor phase to enter a leaching absorption tower for recycling. A single or composite metal oxide product prepared by the solution atomization oxidation has the purity of more than 99 percent, lattice perfection, uniform particle size distribution, simple production process, low cost, non-environmental pollution, and wide industrial application prospect.
Description
Technical field
The present invention relates to method and isolated plant that atomizing and oxidizing solution prepares single or complex metal oxides.
Background technology
Existing preparation method single or complex metal oxides mainly is wet-precipitated-calcination method, be raw material promptly with single or composition metal inorganic salt solution, with ammonium hydrogencarbonate, oxalic acid etc. is precipitation agent, generate precipitations such as subcarbonate, oxalate, after filtration, after washing and the drying, with through high-temperature calcination, obtain oxide powder.This method technical process is long, and the complicated difficult control of process is easy to generate waste gas, waste liquid, causes environmental pollution.Also have vapor phase process and solid phase method.Though vapor phase process makes product purity height, it is few to reunite, and output is lower, and higher to equipment requirements, is difficult for scale operation; The solid phase method equipment used is simple, operation easily, but quality product is not high, is only applicable to require lower industry.Spray pyrolysis is the novel process that proposes in recent years, this technology is adopted by calcining after solution atomization, reaction, the medium adsorbed product again, its technical process is short, operate simpler, " spray pyrolysis prepares the method for nano-powder " disclosed as CN1557715A, but these class methods are because metal salt solution residence time in high-temperature atmosphere is short, and its reaction is not too abundant, and the product crystallization degree is not high; And product still needs through aftertreatment, and the gas that reaction is not produced carries out comprehensive reutilization.
Summary of the invention
The objective of the invention is to overcome above shortcoming, the method and the isolated plant that provide a kind of atomizing and oxidizing solution to prepare single or complex metal oxides.Abundant with realization response, product crystallization degree height; Product is through aftertreatment, can carry out comprehensive reutilization to the gas that reaction produces, but the simple shortened process of environmentally safe and technology, good quality of product, and help automatization, serialization production.
Atomizing and oxidizing solution prepares the method for single or complex metal oxides, may further comprise the steps:
(1) the single or compound soluble metal salts solution of preparation 0.1～3mol/L belongs to 0.1～1% of weight by GOLD FROM PLATING SOLUTION and adds macromolecule dispersing agent, is preheated to 60-80 ℃;
(2) solution after the preheating is input to the pneumatic atomizer in the atomizing and oxidizing solution isolated plant, is 1.0～2.5 * 10 at atomizing pressure
5Atomize under the Pa condition, the disturbing flow device in isolated plant enters into vertical tubular electric furnace again, is 500-950 ℃ in temperature, and behind the air thorough mixing, moment is oxidized to oxide powder;
(3) oxide powder enters the two-stage efficient cyclone separator separation of atomizing and oxidizing solution isolated plant, and oxide powder is collected the back by the continuous pulp discharge device on the cyclonic separator and discharged, and the acid gas in the gas phase enters the drip washing absorption tower and recycles.
Described single or compound soluble metal salts solution is chlorate, nitrate, the vitriol of the single or composition metal of cobalt, nickel, iron, zinc, copper, magnesium, aluminium, calcium, lead, titanium, manganese, bismuth or barium.
Described macromolecule dispersing agent is one or more the mixture among PVP, OP, PVA, the PAA.
The isolated plant that atomizing and oxidizing solution prepares single or complex metal oxides is: be provided with a vertical tubular electric furnace that has 1-6 group electric heating system, in the reaction tubes of vertical tubular electric furnace inside, be provided with disturbing flow device, be provided with sealing cover at the reaction tubes top, sealing cover is provided with the pneumatic atomizer that is connected with feed-pipe, the discharge port of vertical tubular electric furnace bottom is connected with cyclonic separator, and the gas phase of cyclonic separator is connected with the gas absorbing device that reclaims gas.
Compared with prior art, outstanding advantage of the present invention is: (1) solution is through pneumatic atomizer, and atomizing becomes the little droplet of superfine liquid, makes it have higher specific surface area, makes reaction more complete; (2) enter in the vertical tubular electric furnace by the disturbing flow device in the atomizing and oxidizing solution isolated plant, changed the liquid motion track, increased the reaction times, make the product crystal formation more complete; (3) except that adsorption medium, there is not the intervention of other chemical substance, the purity of the product of assurance; (4) entire reaction one step finishes, and significantly shortened process reduces production costs, and has avoided growing up of crystal grain in the follow-up calcination process simultaneously, and the gained diameter of particle is little, is evenly distributed, and does not have and reunites; (5) acid gas in the reaction product is recyclable, no waste produces, environmentally safe, (6), by regulating feed liquor amount, atomization air flow, exhaust fan flow, but the composition of the control of implementation procedure and product, structure, pattern, granularity and distribution thereof.Prepared single or complex metal oxides product purity is greater than 99%, lattice perfection, even particle size distribution.
Description of drawings
Accompanying drawing is atomizing and oxidizing solution isolated plant and process flow diagram.
Embodiment
Embodiment 1:
The atomizing and oxidizing solution isolated plant is to be provided with a vertical tubular electric furnace 1 that has four groups of electric heating system 11-1,11-2,11-3,11-4, is provided with reaction tubes 2 in the inside of vertical tubular electric furnace, is filled with lagging material 6 in reaction tubes 2 outsides.Being provided with spiral catch 7 usefulness of extending vertically in reaction tubes 2 is disturbing flow device, be provided with sealing cover 3 at the reaction tubes top, sealing cover is provided with pneumatic atomizer 4, pneumatic atomizer with held material solution container 9 and be communicated with, by the size of under meter 8 dominant discharge, pressurized air is by air compressor 10 inputs.
The discharge port 5 of vertical tubular electric furnace bottom is connected with 12-2 with two stage cyclone separator 12-1, and powder is collected and discharged by the continuous pulp discharge device on the cyclonic separator 13.Acid gas feeds drip washing absorption tower 14-1 through pipeline, water flows into through recirculated water inlet 19 and carries out drip washing, gas obtains sufficient cooling therein, soluble constituent in the gas is dissolved in the water of condensation, restored acid flows in the acid tank 21 by pipeline, and remaining gas phase fully absorbs through absorption tower, second stage 14-2 again.The waste gas that meets environmental protection standard through pipeline by exhaust fan 20 emptyings that have frequency conversion function.
Embodiment 2:
(1) the CoCl26H2O solution of configuration 1.5mol/L adds OP dispersion agent 0.1g, and it is preheated to 70 ℃;
(2) pneumatic atomizer in the importing atomizing and oxidizing solution isolated plant, atomizing pressure is controlled to be 1.5 * 105Pa, and the disturbing flow device in isolated plant enters into vertical tubular electric furnace again, is 850 ℃ in temperature, with air thorough mixing rear oxidation be oxidate powder
(3) oxide powder enters the two-stage efficient cyclone separator separation of atomizing and oxidizing solution isolated plant, oxide powder after the separation is collected the back by the continuous pulp discharge device on the cyclonic separator and is discharged, and the HCl in the gas phase obtains industrial dilute hydrochloric acid by the aqueous solution spray absorption of two-stage series connection.
The gained powder detects through XRD, and product is the tricobalt tetroxide of single thing phase, analyzes by scanning electron microscope (SEM), and product is equally distributed sphere, and mean particle size is 2.96 μ m.
Embodiment 3:
Co (the NO of configuration 1.5mol/L
3)
26H
2O solution adds PVA dispersion agent 0.1g, it is preheated to 70 ℃ after, import in the atomizing and oxidizing solution isolated plant, atomizing pressure is controlled to be 1.5 * 10
5Pa, temperature of reaction is controlled to be 500 ℃, collects powdered product, the NO in the product gas phase by the two-stage efficient cyclone separator
2Aqueous solution spray absorption by two-stage series connection obtains industrial dilute nitric acid.The gained powder detects through XRD, and product is the tricobalt tetroxide of single thing phase, analyzes by scanning electron microscope (SEM), and product is equally distributed sphere, and mean particle size is 3.59 μ m.
Embodiment 4:
The NiCl of configuration 1.5mol/L
26H
2O solution adds PAA dispersion agent 0.05g, after PVA dispersion agent 0.05g is preheated to 70 ℃ with it, imports in the atomizing and oxidizing solution isolated plant, and atomizing pressure is controlled to be 1.5 * 10
5Pa, temperature of reaction is controlled to be 800 ℃, collects powdered product by the two-stage efficient cyclone separator, and the HCl in the product gas phase obtains industrial dilute hydrochloric acid by the aqueous solution spray absorption of two-stage series connection.The gained powder detects through XRD, and product is the nickel oxide of single thing phase, analyzes by scanning electron microscope (SEM), and product is equally distributed sphere, and mean particle size is 4.25 μ m.
Embodiment 5:
The NiSO of configuration 1.5mol/L
46H
2O solution adds PAA dispersion agent 0.05g, after PVA dispersion agent 0.05g is preheated to 80 ℃ with it, imports in the atomizing and oxidizing solution isolated plant, and atomizing pressure is controlled to be 1.5 * 10
5Pa, temperature of reaction is controlled to be 900 ℃, collects powdered product, the SO in the product gas phase by the two-stage efficient cyclone separator
2Aqueous solution spray absorption by two-stage series connection obtains industrial dilute sulfuric acid.The gained powder detects through XRD, and product is the nickel oxide of single thing phase, analyzes by scanning electron microscope (SEM), and product is equally distributed sphere, and mean particle size is 4.31 μ m.
Embodiment 6:
Co (the NO of configuration 1.0mol/L
3)
26H
2O solution, the NiNO of 1.0mol/L
36H
2O solution, Mn (NO
3)
26H
2O solution, 3.0mol/LiNO
3Solution, be 1: 1: 1 by volume: 1 thorough mixing, add additive PVA 0.1g, it is preheated to 70 ℃ after, import in the atomizing and oxidizing solution isolated plant, atomizing pressure is controlled to be 1.5 * 10
5Pa, temperature of reaction is controlled to be 950 ℃, collects powdered product, the NO in the product gas phase by the two-stage efficient cyclone separator
2Aqueous solution spray absorption by two-stage series connection obtains industrial dilute nitric acid.The gained powder detects through XRD, and product is the complete LiNi of crystalline form
1/3Co
1/3Mn
1/3O
2, to analyze by scanning electron microscope (SEM), product is equally distributed sphere, mean particle size is 4.37 μ m.
Embodiment 7:
The CoCl of configuration 1.65mol/L
26H
2O solution, the NiCl of 0.75mol/L
26H
2O solution, 0.1mol/LFeCl
2Solution, 1: 1: 1 by volume thorough mixing adds additive PAA 0.1g, it is preheated to 70 ℃ after, import in the atomizing and oxidizing solution isolated plant, atomizing pressure is controlled to be 1.5 * 10
5Pa, temperature of reaction is controlled to be 900 ℃, collects powdered product by the two-stage efficient cyclone separator, and the HCl in the product gas phase obtains industrial dilute hydrochloric acid by the aqueous solution spray absorption of two-stage series connection.The gained powder detects through XRD, and product is the complete Fe of crystalline form
33Ni
15Co
2, to analyze by scanning electron microscope (SEM), product is equally distributed sphere, mean particle size is 4.29 μ m.
Embodiment 8:
The AgNO of configuration 0.5mol/L
3Solution adds PAA dispersion agent 0.1g, it is preheated to 80 ℃ after, import in the atomizing and oxidizing solution isolated plant, atomizing pressure is controlled to be 1.5 * 10
5Pa, temperature of reaction is controlled to be 900 ℃, collects powdered product, the NO in the product gas phase by the two-stage efficient cyclone separator
2Aqueous solution spray absorption by two-stage series connection obtains industrial dilute nitric acid.The gained powder detects through XRD, and product is the silver suboxide of single thing phase, analyzes by scanning electron microscope (SEM), and product is equally distributed sphere, and mean particle size is 1.26 μ m.
Embodiment 9:
Ti (the NO of configuration 2.0mol/L
3)
2Solution, the Ba (NO of 2.0mol/L
3)
2Solution, the Ca (NO of 1.0mol/L
3)
2Solution, the Cu (NO of 2.0mol/L
3)
2Solution, 1: 1: 1 by volume: 1 uniform mixing, add OP dispersion agent 0.1g, be preheated to 70 ℃ after, import in the atomizing and oxidizing solution isolated plant, atomizing pressure is controlled to be 1.5 * 10
5Pa, temperature of reaction is controlled to be 600 ℃, collects powdered product, the NO in the product gas phase by the two-stage efficient cyclone separator
2Aqueous solution spray absorption by two-stage series connection obtains industrial dilute nitric acid.The gained powder detects through XRD, and product is the complete Ti of crystalline form
2Ba
2CaCu
2O
x, to analyze by scanning electron microscope (SEM), product is equally distributed sphere, mean particle size is 4.51 μ m.
Claims (2)
1. an atomizing and oxidizing solution prepares the method for single or complex metal oxides, it is characterized in that, may further comprise the steps:
(1) the single or compound soluble metal salts solution of preparation 0.1～3mol/L, described single or compound soluble metal salts solution is chlorate, nitrate, the sulfate liquor of the single or composition metal of cobalt, nickel, iron, zinc, copper, aluminium, manganese, belong to 0.1～1% of weight by GOLD FROM PLATING SOLUTION and add macromolecule dispersing agent, be preheated to 60-80 ℃;
(2) solution after the preheating is input to the pneumatic atomizer in the atomizing and oxidizing solution isolated plant, is 1.0～2.5 * 10 at atomizing pressure
5Atomize under the Pa condition, the disturbing flow device in isolated plant enters into vertical tubular electric furnace again, is 500-950 ℃ in temperature, and behind the air thorough mixing, moment is oxidized to oxide powder;
(3) oxide powder enters the two-stage efficient cyclone separator separation of atomizing and oxidizing solution isolated plant, and oxide powder is collected the back by the continuous pulp discharge device on the cyclonic separator and discharged, and the acid gas in the gas phase enters the drip washing absorption tower and recycles;
Described atomizing and oxidizing solution isolated plant, it is characterized in that, be provided with a vertical tubular electric furnace that has 1-6 group electric heating system, in the reaction tubes of vertical tubular electric furnace inside, be provided with disturbing flow device, be provided with sealing cover at the reaction tubes top, sealing cover is provided with the pneumatic atomizer that is connected with feed-pipe, and the discharge port of vertical tubular electric furnace bottom is connected with cyclonic separator, and the gas phase of cyclonic separator is connected with the gas absorbing device that reclaims gas.
2. atomizing and oxidizing solution according to claim 1 prepares the method for single or complex metal oxides, it is characterized in that, described macromolecule dispersing agent is a kind of among PVP, OP, PVA, the PAA.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102059345B (en) * | 2010-12-08 | 2012-10-31 | 中南大学 | Method for preparing cobalt-nickel metal or alloy powder by solution nebulization method |
| CN102357308B (en) * | 2011-10-19 | 2013-10-23 | 江西稀有稀土金属钨业集团有限公司 | Method for directly preparing anhydrous cobalt chloride powder from cobalt chloride solution |
| CN103143725B (en) * | 2013-03-29 | 2015-08-12 | 赣州远驰新材料有限公司 | The preparation method of rare earth modified tungsten-base alloy powder |
| CN105858724B (en) * | 2016-05-16 | 2017-07-14 | 中南大学 | A kind of method that solution atomization method prepares ultra-fine sb oxide |
| CN106984256B (en) * | 2017-03-30 | 2019-12-17 | 重庆文理学院 | Spray cracking system and application method thereof |
| CN108380199B (en) * | 2018-03-16 | 2020-09-01 | 沈阳理工大学 | Method for preparing europium-titanium composite nano oxide powder |
| CN108658124A (en) * | 2018-03-30 | 2018-10-16 | 中南大学 | The preparation method and system of a kind of bismuth system supercondutive powder |
| CN109835938A (en) * | 2019-03-20 | 2019-06-04 | 金川集团股份有限公司 | A kind of device and its application method for copper nitrate solution spray pyrolysis |
| CN113929153A (en) * | 2021-11-19 | 2022-01-14 | 广东长信精密设备有限公司 | Cobaltosic oxide preparation device |
| CN115121190B (en) * | 2022-06-16 | 2024-04-26 | 中国恩菲工程技术有限公司 | Superfine powder preparation device and method |
| CN115321616B (en) * | 2022-09-23 | 2024-03-29 | 西安稀有金属材料研究院有限公司 | Preparation method of low-cost and particle size controllable nano ruthenium oxide with high specific surface area |
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