CN112110475B - Production process for preparing zinc oxide by using paste precursor - Google Patents
Production process for preparing zinc oxide by using paste precursor Download PDFInfo
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- CN112110475B CN112110475B CN202011012898.6A CN202011012898A CN112110475B CN 112110475 B CN112110475 B CN 112110475B CN 202011012898 A CN202011012898 A CN 202011012898A CN 112110475 B CN112110475 B CN 112110475B
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- aqueous solution
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- formic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Abstract
The invention discloses a production process for preparing zinc oxide by adopting a paste precursor, which comprises the following steps: 1) preparing a zinc chloride aqueous solution on site; 2) preparing a formamide formic acid solution; 3) forming formamide sol; 4) preparing a zinc-containing gel; 5) carbonizing and calcining at low temperature; 6) primary crushing; 7) carbonizing and calcining at medium temperature; 8) and (5) performing secondary crushing to obtain the finished product zinc oxide powder. The invention adopts a meta-acidic zinc chloride aqueous solution, utilizes the certain hydrolyzability of the meta-acidic zinc chloride aqueous solution to mix the meta-acidic zinc chloride aqueous solution with a meta-basic formamide formic acid solution for reaction, slowly hydrolyzes the mixture to generate zinc hydroxide sol, and then adds H2O2The water solution, the surfactant, the PVP and the hydroxyethyl cellulose are aged after being milled by a colloid mill to form a gel system, and due to the introduction of high polymers and other organic matters, two-stage calcination is adopted, the organic matters in the system are calcined into carbon, and then the temperature is increased to completely calcine the carbon, so that a pure zinc oxide product with a small powder density and a high specific surface area is obtained.
Description
Technical Field
The invention relates to the technical field of zinc oxide production, in particular to a production process for preparing zinc oxide by using a paste precursor.
Background
Zinc oxide is a commonly used chemical additive, and is widely applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint, coating, ointment, adhesive, food, batteries, flame retardant and the like. Has the unique performance of activating the rubber accelerator and can be used for manufacturing rubber vulcanized products with wide application. When treating skin wounds, zinc oxide has the function of stopping bleeding and astringing, and is commonly used as adhesive plaster and the like. It can also be used as optical conductor in duplicator and catalyst for methanol synthesis reaction.
The production of zinc oxide can be divided into indirect method zinc oxide, direct method zinc oxide and active zinc oxide according to different production methods. On the other hand, the active zinc oxide has stronger surface polarity and is not easy to be uniformly dispersed in an organic medium, thereby greatly limiting the exertion of the nanometer effect. Therefore, the dispersion and surface modification of the active zinc oxide body become necessary treatment means before the nano material is applied to a matrix.
In the production process of zinc oxide, how to improve the specific surface activity of the product is crucial, and the prior art has various methods aiming at different production processes, but the zinc vapor oxidation method, the solution method or the high-temperature calcination method is covered in any way.
The invention tries to develop from the paste system to research the improvement treatment of the zinc oxide production process.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a production process for preparing zinc oxide by using a paste precursor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a production process for preparing zinc oxide by adopting a paste precursor comprises the following steps:
1) in-situ preparation of zinc chloride aqueous solution: 1kg of ZnCl2Dissolving the mixture into 1L of 1.5 to 2 percent hydrochloric acid aqueous solution, and stirring at a high speed until the mixture is completely dissolved;
2) preparation of formamide formic acid solution: continuously bubbling ammonia gas into formic acid at the temperature of 25-45 ℃;
3) formation of formamide sol: quickly dripping formamide formic acid solution into zinc chloride aqueous solution within 5min, stirring at high speed for 5min, pouring the solution into a crucible, and standing until white sol is formed;
4) preparation of the zinc-containing gel: in the white sol system, 50ml of 20% H is added2O2The preparation method comprises the following steps of uniformly grinding an aqueous solution, 10-20g of a surfactant, 50-60g of PVP and 50-60g of hydroxyethyl cellulose by using a colloid mill, and then putting the mixture back into a crucible to age for 2-3 hours to form a milky gel block which is slightly transparent and is provided with a large amount of bubbles inside;
5) low-temperature carbonization and calcination: calcining the gel block at the temperature of 350-;
6) primary crushing: crushing the foam blocks by a crusher to obtain black powder;
7) medium-temperature carbonization and calcination: calcining the black powder at the temperature of 700-;
8) and (3) secondary crushing: and (4) performing ball milling for 2-3h by using an ultrafine ball mill to obtain the finished zinc oxide powder.
Preferably, the step 2) needs to be carried out in a closed high-pressure tank for ammonia circulation, namely ammonia is added from the lower part of the formic acid liquid surface and is recovered from the upper part of the formic acid liquid surface.
Preferably, the stirring speed of the step 3) is 500-800r/min, so that the mixing is rapid.
Preferably, during the aging process, the white sol polished by the colloid mill has an increasing volume and generates bubble holes, and the crucible in the step 4) is placed in a fume hood for ventilation treatment, so that the volume expansion and the generation of the bubble holes are facilitated.
Preferably, the powder obtained in step 6) is in particular a thin, crumbly, flaky powder which is light in weight and is otherwise prone to being blown away in the wind.
Preferably, the finished zinc oxide powder is specifically a powder with a particle size of less than 100um and a density of 1.3-1.5g/m3High fluffy white powder.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a meta-acidic zinc chloride aqueous solution, utilizes the certain hydrolyzability of the meta-acidic zinc chloride aqueous solution to mix the meta-acidic zinc chloride aqueous solution with a meta-basic formamide formic acid solution for reaction, slowly hydrolyzes the mixture to generate zinc hydroxide sol, and then adds H2O2The method comprises the following steps of (1) aging an aqueous solution, a surfactant, PVP (polyvinyl pyrrolidone) and hydroxyethyl cellulose by using a colloid mill to form a gel system, calcining organic matters in the system into carbon by using two sections due to introduction of macromolecules and other organic matters, and then heating to calcine the carbon completely, so that a pure high-specific-surface zinc oxide product with low powder density is obtained, and the method is a feasible novel zinc oxide production process, has the potential of continuous development and research and optimized production, and is expected to be popularized and used.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
A production process for preparing zinc oxide by adopting a paste precursor is characterized by comprising the following steps:
1) preparing a zinc chloride aqueous solution on site: 1kg of ZnCl2Dissolving the mixture into 1L of 1.5 to 2 percent hydrochloric acid aqueous solution, and stirring at a high speed until the mixture is completely dissolved;
2) preparation of formamide formic acid solution: performing ammonia circulation in a closed high-pressure tank, namely adding ammonia from the lower part of the formic acid liquid surface, recovering ammonia from the upper part of the formic acid liquid surface, and continuously bubbling the ammonia into the formic acid at the temperature of 25-45 ℃;
3) formation of formamide sol: quickly dripping formamide formic acid solution into zinc chloride aqueous solution within 5min, stirring at high speed of 650r/min for 5min, pouring the solution into a crucible, and standing to form white sol;
4) preparation of the zinc-containing gel: in the white sol system, 50ml of 20% H is added2O2The preparation method comprises the following steps of uniformly grinding an aqueous solution, 15g of surfactant, 56g of PVP and 54g of hydroxyethyl cellulose by using a colloid mill, and then putting the mixture back into a crucible to age for 3 hours to form a milky gel block which is slightly transparent and has a large amount of bubbles inside;
5) low-temperature carbonization and calcination: calcining the gel block at 380 ℃, heating at the speed of 50 ℃/min, and keeping the temperature for 30min when the temperature is raised to 380 ℃ to obtain a black foam block of the paint;
6) primary crushing: crushing the foam blocks by a crusher to obtain black powder;
7) medium-temperature carbonization and calcination: calcining black powder at 760 ℃, heating at the rate of 30 ℃/min, keeping the temperature for 3h when the temperature is raised to 760 ℃, and finally cooling along with a furnace to obtain white powder;
8) and (3) secondary crushing: ball milling for 3h by using an ultrafine ball mill to obtain the finished product of zinc oxide powder with the particle size of less than 100um and the density of 1.42g/m3High fluffy white powder.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (1)
1. A production process for preparing zinc oxide by adopting a paste precursor is characterized by comprising the following steps:
1) in-situ preparation of zinc chloride aqueous solution: 1kg of ZnCl2Dissolving the mixture into 1L of 1.5 to 2 percent hydrochloric acid aqueous solution, and stirring at a high speed until the mixture is completely dissolved;
2) preparation of formamide formic acid solution: continuously bubbling ammonia gas into formic acid at the temperature of 25-45 ℃;
3) formation of formamide sol: quickly dripping formamide formic acid solution into zinc chloride aqueous solution within 5min, stirring at high speed for 5min, pouring the solution into a crucible, and standing until white sol is formed;
4) preparation of the zinc-containing gel: in the white sol system, 50ml of 20% H is added2O2The preparation method comprises the following steps of (1) uniformly grinding an aqueous solution, 10-20g of a surfactant, 50-60g of PVP and 50-60g of hydroxyethyl cellulose by using a colloid mill, and then putting the mixture back into a crucible to age for 2-3 hours to form a milky white and slightly transparent gel block with a large amount of bubbles inside;
5) low-temperature carbonization and calcination: calcining the gel block at the temperature of 350-;
6) primary crushing: crushing the foam blocks by a crusher to obtain black powder;
7) medium-temperature carbonization and calcination: calcining the black powder at the temperature of 700-;
8) and (3) secondary crushing: ball milling for 2-3h by using an ultrafine ball mill to obtain finished zinc oxide powder;
in the step 2), ammonia circulation needs to be carried out in a closed high-pressure tank, namely ammonia is added from the lower part of the formic acid liquid surface and is recovered from the upper part of the formic acid liquid surface;
the stirring speed in the step 3) is 500-800 r/min;
in the aging process, the volume of the white sol polished by the colloid mill is continuously increased and bubble holes are generated, and the crucible in the step 4) is placed in a fume hood for ventilation treatment;
the powder obtained in the step 6) is specifically thin and broken flaky powder;
the finished zinc oxide powder has a particle size of less than 100 μm and a density of 1.3-1.5g/m3High fluffy white powder.
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