CN107720808A - A kind of method of low temperature preparation high-purity Nano-class Asia titanium oxide - Google Patents

A kind of method of low temperature preparation high-purity Nano-class Asia titanium oxide Download PDF

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Publication number
CN107720808A
CN107720808A CN201710910232.4A CN201710910232A CN107720808A CN 107720808 A CN107720808 A CN 107720808A CN 201710910232 A CN201710910232 A CN 201710910232A CN 107720808 A CN107720808 A CN 107720808A
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titanium oxide
pelletizing
purity nano
low temperature
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居殿春
邱家用
徐敏人
白妮
陈春钰
张荣良
周夏芝
周磊
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Zhangjiagang Industrial Technology Research Institute of Jiangsu University of Science and Technology
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Zhangjiagang Industrial Technology Research Institute of Jiangsu University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/043—Titanium sub-oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
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  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

This case is related to a kind of method of low temperature preparation high-purity Nano-class Asia titanium oxide, including：Nm-class rutile-type titanium dioxide, reducing agent and wetting agent are subjected to mixing pelletizing, pelletizing is made, then pelletizing is carried out to 2 4h drying and processings at 105 DEG C；Pelletizing after drying is placed in the microwave rotary kiln with non-oxidizing atmosphere and is heated to 700 900 DEG C, 20 60min is incubated, is cooled down under reproducibility airflow function；Pelletizing after reduction is put into ball mill after break process and is ground, the 60min of milling time 20；Powder after grinding is heat-treated, 200 400 DEG C of heat treatment temperature, the 4h of heat treatment time 2, it is final to obtain high-purity Nano-class Asia titanium oxide.This case is realized at a lower temperature prepares high-purity Nano-class Asia titanium oxide by raw material of rutile titanium white powder, and preparation technology flow is short, production efficiency is high, it is easy to accomplish serialization industrial production.

Description

A kind of method of low temperature preparation high-purity Nano-class Asia titanium oxide
Technical field
The present invention relates to a kind of preparation method of sub- titanium oxide, more particularly to a kind of sub- oxidation of low temperature preparation high-purity Nano-class The method of titanium.
Background technology
Sub- titanium oxide is a series of non-stoichiometric titanyl compounds, and its formula is TinO2n-1(n=4~10).1959 Year, X ray scholar Magn é li are first with Detitanium-ore-type TiO2Based on system research has been carried out to this kind of material.Therefore, people This kind of material is referred to as Magn é li phases, referred to as sub- titanium oxide.The research of Magn é li phases in recent years attracts more and more to grind The person of studying carefully pays close attention to, the especially Ti in Magn é li phases4O7Because having stronger corrosion resistance, electrochemical stability and high conductivity Deng advantageous property, shown in fuel cell catalyst carrier, gas sensor, anti-reflective film, photoelectrocatalysis etc. huge Application prospect.
At present, sub- titanium oxide is generally prepared using high-temperature sintering process, and main reducing agent includes H2、NH3、C、Ti、Si、Zr Outstanding problem Deng, high-temperature sintering process be material granule grown up in high-temperature sintering process, coarsening phenomenon it is very prominent, cause material The performance of material substantially reduces because the granular size of material, porosity, crystallinity etc. directly affect its optics, electromagnetism and The characteristic of electrochemistry.To improve the topographical property of material, scientific research personnel develops laser ablation method, collosol and gel-sintering in succession Method etc., the control to material morphology and size is realized to a certain extent, reduce reduction temperature requirement, but not from basic Upper to solve the problems, such as in material preparation process due to particle growth caused by higher sintering temperature, part is listed in table 1 to be had Representational sub- titanium oxide preparation method.
The sub- titanium oxide preparation technology of Magn é li phases of table 1
As it can be seen from table 1 the preparation technology of sub- titanium oxide is complex, reaction temperature is high, reaction time length, and reacts There are conclusive influence in temperature, reaction time to the microscopic appearance of sub- titanium oxide, granular size, in addition, the physics of sub- titanium oxide With chemical property as accurate sub- oxygen state (n values) significantly changes.
In preparation process, sub- titanium oxide is easily influenceed by reaction condition, so reaction condition must be accurately controlled, in favor of Product expected from generation.Influenceing the factor of reducing degree and product component mainly includes：Reactant composition, reducing agent are in the feed Decentralization, particle size, material density, reaction temperature and reaction time etc..
The content of the invention
For technical problem present in prior art, the purpose of this case, which is to provide one kind, to be prepared at a lower temperature The method of high-purity Nano-class Asia titanium oxide, to simplify preparation technology flow, and realize serialization industrial production.
To achieve the above object, this case is achieved through the following technical solutions：
A kind of method of low temperature preparation high-purity Nano-class Asia titanium oxide, it includes：
Step 1) ball processed：Nm-class rutile-type titanium dioxide, reducing agent and wetting agent are mixed, pelletizing, ball is made Footpath 2-5cm pelletizing, then pelletizing is subjected to 2-4h drying and processings at 105 DEG C；The sphere diameter of pelletizing is too big or too small is unfavorable for Reduction process it is quick, be smoothed out；On the one hand drying is used to improve pellet strength, ensure to be not easily broken in transport process, separately On the one hand prevent pelletizing in rapid heating condition due to being burst caused by the volatilization expansion of flux moment；
Step 2) reduces：Pelletizing after drying is placed in the microwave rotary kiln with non-oxidizing atmosphere and is heated to 700- 900 DEG C, 20-60min is incubated, is cooled down after the completion of reaction under reproducibility airflow function；Reduction furnace is the stove using microwave as thermal source Body, the type of furnace is rotary kiln, and reduction furnace only has forward part to have heating function, and rear part, can be in stove simultaneously without heating function Realize two continuous processes of heating and cooling；Can reach from the reduction furnace using microwave as thermal source be rapidly heated and cool will Ask, prevent due to heating or temperature fall time long caused particle growth, coarsening phenomenon；The unsuitable too high or mistake of heating-up temperature Low, the too high reaction product that easily causes is grown up and is roughened；Too low reaction speed to be caused to slow down, production efficiency is low, therefore adds Hot temperature needs to control in suitable scope；Soaking time is unsuitable long or too short, long to easily cause growing up for reaction product And roughening；Too short that reaction can be caused incomplete, reaction product is not pure, therefore soaking time needs to control in suitable scope It is interior；
Step 3) is ground：Pelletizing after reduction is put into ball mill after break process and is ground, milling time 20-60min；Milling time is unsuitable long or too short, long energy consumption to be caused to increase, and production cost improves, too short to cause to grind Mill is uneven, particle size distribution concentration degree difference etc., therefore milling time should be preferably controlled in 20-60min；
Step 4) is heat-treated：Powder after grinding is heat-treated, 200-400 DEG C of heat treatment temperature, heat treatment time 2-4h, it is final to obtain high-purity Nano-class Asia titanium oxide.The purpose of heat treatment is further to improve its degree of purity.
Preferably, the method for described low temperature preparation high-purity Nano-class Asia titanium oxide, wherein, the rutile titanium dioxide The particle diameter of powder is no more than 100nm.
Preferably, the method for described low temperature preparation high-purity Nano-class Asia titanium oxide, wherein, the reducing agent is selected from ammonia At least one of base acid.
Preferably, the method for described low temperature preparation high-purity Nano-class Asia titanium oxide, wherein, the wetting agent is dissolving There are the organic solution or the aqueous solution of the reducing agent, the accounting of reducing agent is no more than 5wt% in the wetting agent.
Preferably, the method for described low temperature preparation high-purity Nano-class Asia titanium oxide, wherein, in single pelletizing, institute The gross mass for stating reducing agent accounts for the 20-50% of single pellet quality.
Preferably, the method for described low temperature preparation high-purity Nano-class Asia titanium oxide, wherein, the non-oxidizing atmosphere Selected from reducing atmosphere, inert atmosphere or its combination.The gas being passed through in stove is reducibility gas, after can not only cooling down reduction Product, may additionally facilitate the reduction of pelletizing, strengthen reduction effect, accelerate reduction process, improve production efficiency.Reducing atmosphere and Reproducibility air-flow includes but is not limited to hydrogen, ammonia, carbon monoxide；Inert atmosphere includes but is not limited to argon gas, helium, nitrogen.
Preferably, the method for described low temperature preparation high-purity Nano-class Asia titanium oxide, wherein, the reducing agent is selected from day Winter acid amides, glutamine or its combination.
The beneficial effects of the invention are as follows：The method that this case uses can realize at a lower temperature using rutile titanium white powder as Raw material prepares high-purity Nano-class Asia titanium oxide, and preparation technology flow is short, production efficiency is high, it is easy to accomplish continuous chemical industry Production.
Brief description of the drawings
Fig. 1 is the process chart of this case low temperature preparation high-purity Nano-class Asia titanium oxide.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to specification text Word can be implemented according to this.
Embodiment 1
Nm-class rutile-type titanium dioxide 8000g is weighed, is incorporated 3000g asparagines and 1000g concentration as 5% asparagus fern Amide aqueous solution, balling-up is suppressed after mixing, pelletizing is dried into 3h at 105 DEG C；Dried pelletizing is sent into microwave revolution again In kiln, the temperature setting of microwave rotary kiln bringing-up section is 850 DEG C, heat time 30min, is quickly cooled down after the completion of reaction；Reduction Pelletizing afterwards is put into ball mill after break process to be ground, milling time 50min.Finally by the nanometer after grinding The sub- titanium oxide of level is heat-treated, 250 DEG C, heat treatment time 3h of heat treatment temperature, final to obtain high cleanliness nanoscale Asia oxygen Change titanium.
TiO2Reduction mechanism is as follows：
TiO2+C4H8N2O3→Ti4O7+CO2+H2O+N2…...(1)
High cleanliness nanoscale Asia titanium oxide analysis result is：Sub- titanium oxide content is 98.5%, wherein Ti4O7Content is 95.2%.
Embodiment 2
Nm-class rutile-type titanium dioxide 8000g is weighed, is incorporated 3000g glutamine and 1000g concentration as 5% paddy ammonia Amide aqueous solution, balling-up is suppressed after mixing, pelletizing is dried into 3h at 105 DEG C；Dried pelletizing is sent into microwave revolution again In kiln, the temperature setting of microwave rotary kiln bringing-up section is 800 DEG C, heat time 40min, is quickly cooled down after the completion of reaction；Reduction Pelletizing afterwards is put into ball mill after break process to be ground, milling time 50min.Finally by the nanometer after grinding The sub- titanium oxide of level is heat-treated, 250 DEG C, heat treatment time 3h of heat treatment temperature, final to obtain high cleanliness nanoscale Asia oxygen Change titanium.
TiO2Reduction mechanism is as follows：
TiO2+C5H10N2O3→Ti4O7+CO2+H2O+N2…...(2)
High cleanliness nanoscale Asia titanium oxide analysis result is：Sub- titanium oxide content is 98.3%, wherein Ti4O7Content is 94.5%.
Embodiment 3
Weigh nm-class rutile-type titanium dioxide 8000g, supplying 1500g asparagines, 1500g glutamine and 1000g Containing (asparagine of 2.5% glutamine+2.5%) aqueous solution, balling-up is suppressed after mixing, pelletizing is dried at 105 DEG C 3h；Dried pelletizing is sent into microwave rotary kiln again, the temperature setting of microwave rotary kiln bringing-up section is 750 DEG C, during heating Between 60min, quickly cooled down after the completion of reaction；Pelletizing after reduction is put into ball mill after break process to be ground, and is ground Consume time as 50min.Finally the nanoscale Asia titanium oxide after grinding is heat-treated, 250 DEG C of heat treatment temperature, during heat treatment Between 3h, it is final to obtain high cleanliness nanoscale Asia titanium oxide.
TiO2Reduction mechanism is as follows：
TiO2+C4H8N2O3+C5H10N2O3→Ti4O7+CO2+H2O+N2…...(3)
High cleanliness nanoscale Asia titanium oxide analysis result is：Sub- titanium oxide content is 99.1%, wherein Ti4O7Content is 95.5%.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited In specific details and shown here as the legend with description.

Claims (7)

  1. A kind of 1. method of low temperature preparation high-purity Nano-class Asia titanium oxide, it is characterised in that including：
    Step 1) ball processed：Nm-class rutile-type titanium dioxide, reducing agent and wetting agent are mixed, pelletizing, sphere diameter 2- is made 5cm pelletizing, then pelletizing is subjected to 2-4h drying and processings at 105 DEG C；
    Step 2) reduces：Pelletizing after drying is placed in the microwave rotary kiln with non-oxidizing atmosphere and is heated to 700-900 DEG C, 20-60min is incubated, is cooled down after the completion of reaction under reproducibility airflow function；
    Step 3) is ground：Pelletizing after reduction is put into ball mill after break process and is ground, milling time 20- 60min；
    Step 4) is heat-treated：Powder after grinding is heat-treated, 200-400 DEG C of heat treatment temperature, heat treatment time 2-4h, It is final to obtain high-purity Nano-class Asia titanium oxide.
  2. 2. the method for low temperature preparation high-purity Nano-class Asia titanium oxide as claimed in claim 1, it is characterised in that the rutile The particle diameter of type titanium dioxide is no more than 100nm.
  3. 3. the method for low temperature preparation high-purity Nano-class Asia titanium oxide as claimed in claim 1, it is characterised in that the reducing agent Selected from least one of amino acid.
  4. 4. the method for low temperature preparation high-purity Nano-class Asia titanium oxide as claimed in claim 1, it is characterised in that the wetting agent For organic solution or the aqueous solution dissolved with the reducing agent, the accounting of reducing agent is no more than 5wt% in the wetting agent.
  5. 5. the method for low temperature preparation high-purity Nano-class Asia titanium oxide as claimed in claim 4, it is characterised in that in single pelletizing In, the gross mass of the reducing agent accounts for the 20-50% of single pellet quality.
  6. 6. the method for low temperature preparation high-purity Nano-class Asia titanium oxide as claimed in claim 1, it is characterised in that described non-oxide Property atmosphere be selected from reducing atmosphere, inert atmosphere or its combination.
  7. 7. the method for low temperature preparation high-purity Nano-class Asia titanium oxide as claimed in claim 3, it is characterised in that the reducing agent Selected from asparagine, glutamine or its combination.
CN201710910232.4A 2017-09-29 2017-09-29 A kind of method of low temperature preparation high-purity Nano-class Asia titanium oxide Pending CN107720808A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109110804A (en) * 2018-11-09 2019-01-01 攀枝花学院 Sub- titanium oxide of high-purity Magn é li phase and preparation method thereof
CN112266242A (en) * 2020-11-19 2021-01-26 张希君 Method for preparing spherical rutile particles by using rutile with size less than 200 meshes as main raw material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172124A (en) * 2013-04-17 2013-06-26 新疆大学 Method for preparing ferric oxide three-dimensional nanostructure through solid-state chemical reaction
CN106865602A (en) * 2017-03-02 2017-06-20 攀枝花学院 The preparation method of graphite titanium suboxide composite
CN106915767A (en) * 2017-03-03 2017-07-04 陕西科技大学 A kind of holey Magneli phases Asia titania meterial and its low temperature preparation method
CN106976905A (en) * 2017-03-07 2017-07-25 中国科学院上海硅酸盐研究所 The sub- titanium oxide and its controllable method for preparing of core shell structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172124A (en) * 2013-04-17 2013-06-26 新疆大学 Method for preparing ferric oxide three-dimensional nanostructure through solid-state chemical reaction
CN106865602A (en) * 2017-03-02 2017-06-20 攀枝花学院 The preparation method of graphite titanium suboxide composite
CN106915767A (en) * 2017-03-03 2017-07-04 陕西科技大学 A kind of holey Magneli phases Asia titania meterial and its low temperature preparation method
CN106976905A (en) * 2017-03-07 2017-07-25 中国科学院上海硅酸盐研究所 The sub- titanium oxide and its controllable method for preparing of core shell structure

Non-Patent Citations (1)

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TOMOHIRO TAKEUCHI等: "Synthesis of Ti4O7 Nanoparticles by Carbothermal Reduction Using Microwave Rapid Heating", 《CATALYSTS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109110804A (en) * 2018-11-09 2019-01-01 攀枝花学院 Sub- titanium oxide of high-purity Magn é li phase and preparation method thereof
CN109110804B (en) * 2018-11-09 2021-01-12 攀枝花学院 High-purity magneli phase titanium suboxide and preparation method thereof
CN112266242A (en) * 2020-11-19 2021-01-26 张希君 Method for preparing spherical rutile particles by using rutile with size less than 200 meshes as main raw material

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