CN111056569A - Method for preparing nano zirconium oxide by alcohol method - Google Patents

Method for preparing nano zirconium oxide by alcohol method Download PDF

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CN111056569A
CN111056569A CN202010071779.1A CN202010071779A CN111056569A CN 111056569 A CN111056569 A CN 111056569A CN 202010071779 A CN202010071779 A CN 202010071779A CN 111056569 A CN111056569 A CN 111056569A
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reaction
reaction kettle
temperature
alcohol
zirconia
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CN111056569B (en
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黄伯璞
焦海坡
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Mianzhu Jin Kun Chemical Co Ltd
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Mianzhu Jin Kun Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a method for preparing nano-zirconia by an alcohol method, which comprises the step of reacting ZrCl4And anhydrous n-butyl alcohol as initial reactant to produce zirconium butoxide in a reaction kettle, and the reaction condition is controlled to produce nanometer zirconia under the action of mineralizer calcium chloride4The nano zirconia is only required to react in the same reaction kettle by controlling the process conditions, and all reactions are completed in the same reaction vessel, so that the method is favorable for industrial production; ZrCl4The hydrogen chloride in the system is removed through a nitrogen displacement method in the reaction with the anhydrous n-butyl alcohol, so that the reaction for generating the n-butyl alcohol zirconium is fast and thorough, ammonia gas or sodium alkoxide does not need to be additionally introduced into the system, and the method is simple in process, safe and reliable; the reaction is completed under the action of mineralizer calcium chloride by microwave heating, high-temperature calcination is not needed, and the finished product can be obtained only by drying under the condition of low temperature, wherein the grain diameter of the obtained product is 2-6nm, the grain growth is complete, and the grains are completeSmall size, uniform distribution and no agglomeration.

Description

Method for preparing nano zirconium oxide by alcohol method
Technical Field
The invention relates to the field of zirconia preparation, in particular to a method for preparing nano zirconia by an alcohol method.
Background
The nanometer zirconia powder is an important raw material for preparing zirconia nanometer ceramics and refractory materials. The zirconia ceramic has excellent high temperature resistance, high temperature conductivity, high hardness (7 Mohs scale), high temperature strength, high toughness, high heat stability, high chemical stability, high corrosion resistance and stable performance. The product can be used as a high-temperature heating body, such as a rocket nose cone, an electrode of a magnetofluid generator and an engine part, and also can be used as an ultrahigh-temperature refractory material, a grinding material, a cutting tool, electronic ceramics (high-pressure and high-frequency ceramics), biological ceramics and the like. The product is also used for manufacturing kiln furniture and crucibles which require higher use temperature and chemical purity, and compared with corundum kiln furniture, the zirconia can provide good use performance because of higher inertia degree to vessels. The crucible made of zirconia can be used for smelting potassium, sodium, iron and metals such as platinum, palladium, rhodium and the like. Zirconia tubes using induction heating are mainly used for the manufacture of glass fibers. In addition, zirconia is used in the enamel industry to improve the acid resistance of enamels; in the glass industry for improving its alkali resistance and for producing glasses with good chemical and thermal stability; are used in the metallurgical industry to make various zirconium-containing alloys. The existing process for preparing the nano zirconia has various methods, such as a hydrothermal method, a precipitation method, an inverse micelle method, chemical vapor deposition, a supercritical drying method, a freeze-drying method, a coacervation method and the like, and the existing preparation method has the problems of complex process, high preparation requirement, easy agglomeration of prepared nano powder, poor uniformity and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing nano-zirconia by an alcohol method, wherein ZrCl is used for reaction4And anhydrous n-butyl alcohol as initial reactant to produce zirconium butoxide in a reaction kettle, and under the action of mineralizer calcium chloride, the zirconium butoxide under high temperature and high pressure is reacted in n-butyl alcohol solvent system to produce nano zirconia4The nano zirconia can be prepared only by controlling the process conditions in the same high-temperature high-pressure reaction kettle and finally filtering, washing and drying the precipitate at low temperature, and all reactions are completed in the same reaction vessel, so that the method is favorable for industrial production; ZrCl4The hydrogen chloride in the system is removed through a nitrogen displacement method in the reaction with the anhydrous n-butyl alcohol, so that the reaction for generating the n-butyl alcohol zirconium is fast and thorough, ammonia gas or sodium alkoxide does not need to be additionally introduced into the system, and the method is simple in process, safe and reliable; the reaction is completed under the action of mineralizer calcium chloride by microwave heating, high-temperature calcination is not needed, and drying is only needed under the low-temperature condition to obtain the calcium chloride catalystThe obtained product has the grain diameter of 2-6nm, complete crystal grain development, small grain size, uniform distribution and no agglomeration.
The purpose of the invention is realized by the following technical scheme:
the method for preparing the nano zirconia by the alcohol method is characterized by comprising the following process steps:
s1, adding a certain amount of ZrCl into the reaction kettle4Adding excessive anhydrous n-butyl alcohol which is dried and rectified by anhydrous magnesium sulfate, heating and raising the temperature to control the reaction temperature to be 100-fold-120 ℃, preserving the temperature for a period of time, introducing nitrogen into the liquid in the reaction kettle while the reaction is carried out, replacing the gas in the reaction kettle by the nitrogen, and introducing the nitrogen into the liquid to replace the hydrogen chloride gas in the system on one hand, thereby playing a role in stirring on the other hand, forming numerous reaction interfaces by a plurality of micro bubbles and promoting the effective reaction;
s2, adding a mineralizer CaCl into the reaction kettle after the reaction in the step S1 is finished2Introducing a certain amount of nitrogen into the reaction kettle again, sealing the reaction kettle, heating by using microwave, continuously increasing the pressure in the reaction kettle until the system temperature is 180-plus-200 ℃ and the pressure is more than 1.2MPa, and keeping the temperature and the pressure for 1-2 h;
s3, cooling and filtering after the reaction is finished, adding a proper amount of deionized water into the filtered product, stirring for 10-20min, filtering for the second time, and drying the filtered product at low temperature of 350 ℃ at 300 ℃ to obtain the final product.
Further, ZrCl in the step S14The mass ratio of the magnesium sulfate to the anhydrous magnesium sulfate is 1:19.2-1: 28.5.
Further, when the temperature in the step S1 is increased to 100-120 ℃, the temperature is maintained for 3-5 h.
Further, ZrCl is added into the reaction kettle in the step S24：CaCl2Adding a mineralizer CaCl with the mass ratio of 1:0.5-1:12。
Further, the microwave heating power in the step S2 is 500-.
Further, the heating temperature rise rate in the step S2 is controlled to be 5-6 ℃/min.
Further, in the step S3, the temperature is reduced to room temperature by water cooling through a coil pipe arranged in the reaction kettle.
The invention has the beneficial effects that:
1. the preparation method provided by the invention firstly leads ZrCl to be replaced by nitrogen4The method has the advantages that the method can effectively remove hydrogen chloride generated in the system to enable the reaction to move towards the positive reaction direction by reacting with anhydrous n-butyl alcohol to generate zirconium butoxide, the reaction can be carried out quickly and thoroughly, ammonia gas or sodium alkoxide does not need to be additionally introduced into the system, and the method is simple in process, safe and reliable;
2. n-Butanol Anhydrous and ZrCl4After reacting for a period of time, adding a mineralizer calcium chloride into the reaction kettle, carrying out further reaction under the conditions of high temperature and high pressure by microwave heating to generate nano-zirconia, wherein all reactions are carried out in the same n-butyl alcohol solvent system and the same reaction vessel, and the reaction process does not need to carry out other treatments and change the reaction vessel, thereby being beneficial to reducing the cost and improving the efficiency of industrial production;
3. the mineralizer calcium chloride is added into the n-butyl alcohol solvent system to finally generate the nano zirconia, so that the reaction condition is easy to control and the safety coefficient is high;
4. the product prepared by the preparation method provided by the invention has the advantages of complete crystal grain development, small particle size, uniform distribution, no agglomeration, no need of high-temperature calcination, and capability of obtaining a finished product only by drying under a low-temperature condition.
Detailed Description
The technical solutions of the present invention are described in further detail below, but the scope of the present invention is not limited to the following.
Example 1
The method for preparing the nano zirconia by the alcohol method is characterized by comprising the following process steps:
s1, adding a certain amount of ZrCl into the reaction kettle4Adding excessive anhydrous n-butanol dried and rectified by anhydrous magnesium sulfate, heating to 100 deg.C, maintaining for 5 hr, and ZrCl4The mass ratio of the anhydrous magnesium sulfate to the anhydrous magnesium sulfate is 1:19.2, and the reaction is carried outIntroducing nitrogen into the liquid in the reaction kettle, and replacing the gas in the reaction kettle by the nitrogen;
s2, after the reaction of the step S1 is finished, ZrCl is added into the reaction kettle4：CaCl2Adding a mineralizer CaCl with the mass ratio of 1:0.52Introducing a certain amount of nitrogen into the reaction kettle again, sealing the reaction kettle, heating by using microwave, wherein the microwave heating power is 500W, the heating temperature rise rate is controlled at 5 ℃/min, the pressure in the reaction kettle is continuously increased at the moment until the temperature of the system is 180 ℃ and the pressure is 1.24MPa, and keeping the temperature and the pressure for 2 hours;
and S3, after the reaction is finished, cooling by water cooling through a coil arranged in the reaction kettle, carrying out suction filtration, adding a proper amount of deionized water into the suction filtration product, stirring for 10min, carrying out secondary suction filtration, and drying the secondary suction filtration product at a low temperature of 300 ℃ to obtain the final product.
Example 2
The method for preparing the nano zirconia by the alcohol method is characterized by comprising the following process steps:
s1, adding a certain amount of ZrCl into the reaction kettle4Adding excessive anhydrous n-butanol dried and rectified by anhydrous magnesium sulfate, heating to 110 deg.C, maintaining for 4 hr, and ZrCl4The mass ratio of the anhydrous magnesium sulfate to the anhydrous magnesium sulfate is 1:24, nitrogen is introduced into liquid in the reaction kettle while the reaction is carried out, and gas in the reaction kettle is replaced by the nitrogen;
s2, after the reaction of the step S1 is finished, ZrCl is added into the reaction kettle4：CaCl2Adding a mineralizer CaCl with the mass ratio of 1:0.82Introducing a certain amount of nitrogen into the reaction kettle again, sealing the reaction kettle, heating by using microwave, wherein the microwave heating power is 650W, the heating temperature rise rate is controlled at 5.5 ℃/min, the pressure in the reaction kettle is continuously increased at the moment until the temperature of the system is 190 ℃ and the pressure is 1.32MPa, and keeping the temperature and the pressure for 1.5 h;
and S3, after the reaction is finished, cooling by water cooling through a coil arranged in the reaction kettle, carrying out suction filtration, adding a proper amount of deionized water into the suction filtration product, stirring for 15min, carrying out secondary suction filtration, and drying the secondary suction filtration product at a low temperature of 325 ℃ to obtain the final product.
Example 3
The method for preparing the nano zirconia by the alcohol method is characterized by comprising the following process steps:
s1, adding a certain amount of ZrCl into the reaction kettle4Adding excessive anhydrous n-butanol dried and rectified by anhydrous magnesium sulfate, heating to 120 deg.C, maintaining for 3 hr, and ZrCl4The mass ratio of the anhydrous magnesium sulfate to the anhydrous magnesium sulfate is 1:28.5, nitrogen is introduced into liquid in the reaction kettle while the reaction is carried out, and gas in the reaction kettle is replaced by the nitrogen;
s2, after the reaction of the step S1 is finished, ZrCl is added into the reaction kettle4：CaCl2Adding a mineralizer CaCl with the mass ratio of 1:12Introducing a certain amount of nitrogen into the reaction kettle again, sealing the reaction kettle, heating by using microwave, wherein the microwave heating power is 800W, the heating temperature rise rate is controlled at 6 ℃/min, the pressure in the reaction kettle is continuously increased at the moment until the temperature of the system is 200 ℃ and the pressure is 1.51MPa, and keeping the temperature and the pressure for 1 h;
and S3, after the reaction is finished, cooling by water cooling through a coil arranged in the reaction kettle, carrying out suction filtration, adding a proper amount of deionized water into the suction filtration product, stirring for 20min, carrying out secondary suction filtration, and drying the secondary suction filtration product at a low temperature of 350 ℃ to obtain the final product.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. The method for preparing the nano zirconia by the alcohol method is characterized by comprising the following process steps:
s1, adding a certain amount of ZrCl into the reaction kettle4Then addAdding excessive anhydrous n-butyl alcohol which is dried and rectified by anhydrous magnesium sulfate, heating and raising the temperature to control the reaction temperature to be 100-fold-120 ℃, preserving the temperature for a period of time, introducing nitrogen into liquid in the reaction kettle while the reaction is carried out, replacing gas in the reaction kettle by using the nitrogen, and introducing the nitrogen into the liquid to replace hydrogen chloride gas in the system on one hand, so that the stirring effect is achieved on the other hand, and a plurality of micro bubbles form an infinite number of reaction interfaces to promote the effective reaction;
s2, adding a mineralizer CaCl into the reaction kettle after the reaction in the step S1 is finished2Introducing a certain amount of nitrogen into the reaction kettle again, sealing the reaction kettle, heating by using microwave, continuously increasing the pressure in the reaction kettle until the system temperature is 180-plus-200 ℃ and the pressure is more than 1.2MPa, and keeping the temperature and the pressure for 1-2 h;
s3, cooling and filtering after the reaction is finished, adding a proper amount of deionized water into the filtered product, stirring for 10-20min, filtering for the second time, and drying the filtered product at low temperature of 350 ℃ at 300 ℃ to obtain the final product.
2. The method for preparing nano zirconia by the alcohol method according to claim 1, wherein ZrCl is adopted in the step S14The mass ratio of the magnesium sulfate to the anhydrous magnesium sulfate is 1:19.2-1: 28.5.
3. The method for preparing nano zirconia by using the alcohol method as claimed in claim 1, wherein the temperature in the step S1 is raised to 100-120 ℃ and is kept for 3-5 h.
4. The method for preparing nano-zirconia by the alcohol process according to claim 1, wherein ZrCl is added into the reaction kettle in the step S24：CaCl2Adding a mineralizer CaCl with the mass ratio of 1:0.5-1:12。
5. The method as claimed in claim 1, wherein the microwave heating power in step S2 is 500-800W.
6. The method for preparing nano zirconia by the alcohol method according to claim 1, wherein the heating temperature rise rate in the step S2 is controlled to be 5-6 ℃/min.
7. The method for preparing nano zirconia by using the alcohol method according to claim 1, wherein the temperature of the reaction kettle in the step S3 is reduced to room temperature by water cooling through a coil pipe arranged inside the reaction kettle.
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