CN108166051A - A kind of morphology controllable potassium hexatitanate powder crystal material and its low energy consumption preparation method - Google Patents
A kind of morphology controllable potassium hexatitanate powder crystal material and its low energy consumption preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of morphology controllable potassium hexatitanate powder crystal material and its low energy consumption preparation methods.Technical solution：Titanium precursor will first be contained to add in propylene oxide (PO) alcohol solution, collosol and gel dynamic process is driven by epoxy reaction, forms the titanium dioxide alcogel of dispersing cellular, go out nano-TiO by drying, grinding, calcining pre-synthesis2.Then by nano-TiO obtained2Powder mixes according to a certain ratio with potassium-containing compound, adds in a small amount of deionized water, and stirring, ultrasonic disperse and dry calcined after different temperatures can obtain the sheet of morphology controllable and crystal whisker-shaped potassium hexatitanate series powder crystal material.Compared with tradition prepares potassium hexatitanate material technology, the present invention greatly reduces manufacturing cost and can prepare the sheet of morphology controllable, crystal whisker-shaped potassium hexatitanate, and is substantially reduced potassium hexatitanate powder crystal synthesis temperature, simple for process, easy to operate, low energy consumption；The powder crystal material crystalline of preparation is good, morphology controllable, and yield is high, widely used.
Description
Technical field
The invention belongs to the material engineering such as function reinforcing material, friction material, heat-barrier material, catalyst and carrier technology necks
Domain is specifically related to a kind of morphology controllable potassium hexatitanate powder crystal material and its low energy consumption preparation method.
Background technology
Potassium titanate (K2O·nTiO2, n=2,4,6,8) and material is one kind by TiO6Octahedron passes through common rib and coplanar formation
Tunnel structure, K+It is not easy to dissolve out among tunnel, so potassium titanate material has good chemical stability and physical mechanical
Performance, such as wear-resisting, corrosion resistance, heat resistance and lower thermal conductivity.Dupont Materials Co., Ltd grinds from the fifties in last century
Since sending out the material, potassium titanate functional material is in environmental treatment agent, ion exchange material, new energy associated materials such as photocatalytic water
Catalyst for preparing hydrogen, lithium ion battery porous diffusion barrier material, automotive brake pads composite friction material, plastic reinforcement and every
The fields such as hot material have extensive market application foreground.
Since potassium titanate material has sheet, the stratiform microstructure different with tunnel-like, practical powder crystal form is normal
Show as different nanobelts, nano wire and nanometer rods and needle-shaped and crystal whisker-shaped aggregate form.Wherein, made extensively
Potassium hexatitanate (K2Ti6O13) crystal whisker materials, the Representative synthetic procedures reported at present have very much, such as hydro-thermal method, fusion method, help
(the references such as solvent method, sol-gel method, sintering process, KDC methods, chilling sintering crystallisation, liquid-phase precipitation method：Wang Hui, Shang Shaoming,
Low energy consumption prepares technique study [J] application chemical industry of crystal whisker of hexa potassium titanate, 2010,39 (12):1878-1881；Xiaoming
Sun, Xing Chen, and Yadong Li, Large-Scale Synthesis of Sodium and Potassium
Titanate Nanobelts, Inorg.Chem.2002,41：4996-4998).In numerous preparation methods, sintering process has work
Industry high income, advantage of lower cost advantage, and suitable industrialized production simple for process (reference：Yang Li,Haiyang Yu,
YangYang, Feng Zheng, Hongwei Ni, Mei Zhang, Min Guo, Synthesis of potassium
hexatitanate whiskers with high thermal stability from Ti-bearing electric
Arc furnace molten slag [J], Ceramics International, 2016,42：11294–11302).But due to
In solid sintering technology production crystal whisker of hexa potassium titanate preparation process, usually using granular titanium oxide or containing Titanium slag and hydrogen
Potassium oxide or potassium carbonate are raw material, and 900-1100 DEG C of high temperature range long-time heat preservation can obtain required product.High energy in the process
High production cost caused by consumption hinders the large-scale application (reference of crystal whisker of hexa potassium titanate industrially：Wang Xin,Liu
Shuangjin,Qi Yumin,et al.Behavior of potassium titanate whisker in simulated
body fluid[J].2014,(135):139-142.).Meanwhile generally use rutile-type in potassium hexatitanate raw materials for production
TiO2Or metatitanic acid, (the reference of the more difficult stability contorting of physicochemical property：Liu Chunyan, Liu Yumin paint beautiful jade, are raw material sintering etc., metatitanic acid
Method prepares ultra-fine crystal whisker of hexa potassium titanate [J] China YouSe Acta Metallurgica Sinicas, 2008,18 (12):2007).Chinese patent
CN100577896C discloses a kind of crystal whisker of hexa potassium titanate and its hydrothermal preparing process, and the crystal whisker of hexa potassium titanate diameter prepared is about
It between 200-500nm, is about between 20000-30000 μm, major diameter is bigger, and whisker yield is 83% or so, but it is tested
That raw material is selected is the Detitanium-ore-type TiO of technical grade2With hydrothermal synthesis technology.The method be unfavorable for magnanimity prepare it is cost-effective
Product.Xu Yan Ji et al. is studied the synthesis form and mechanism of nanometer potassium hexatitanate, demonstrates Nano titanium dioxide and is
Raw material can reduce potassium hexatitanate calcining synthesis temperature (reference：Xu Yanji, Xu Mingxia, Shen Yutian, etc. nanometer K2Ti6O13W is closed
Morphology evolution and growth mechanism [J] Journal of Inorganic Materials in, 2006,6 (21)：1325-1332.).Chinese patent
CN106048727A discloses the method that one step of combustion method prepares crystal whisker of hexa potassium titanate, and selection metatitanic acid k particle and titanium dioxide are
Raw material mixes respectively with activated carbon, acetylene, benzoic acid fuel, and heating about 15min prepares crystal whisker of hexa potassium titanate.The invention skill
Though art improves preparation method, a step directly synthesizes and generated time is short, and six metatitanic acids are prepared using fuel combustions such as activated carbons
Potassium whisker, the discharge of the carbon dioxide isothermal chamber gas in reaction process are unfavorable for environmentally protective.Chinese patent
CN101962808A discloses a kind of energy that raising potassium titanate crystal whisker material is integrated by residual heat from kiln furnace recovery technology and uses effect
Rate, but the complex technical process that the inventive technique uses, the period is long, and equipment investment is big, is unfavorable for industrialization promotion.
Potassium titanate crystal whisker material is prepared compared to solid reaction process, sol-gel technique is a kind of low temperature, can simply obtain
A kind of material preparation technology of high purity chemical composition.It is forged using 630 DEG C of also low 350 DEG C than molten-salt growth method of sol-gel technique
Burning condition obtains the (reference of potassium titanate material：K.T.Jung and Y.G.Shul, Synthesis of high surface
Area potassium hexatitanate powders by sol-gel method [J], Journal of Sol-Gel
Science and Technology 1996,6：227~233).It, can using same method combination ceramic roasting technology
Obtain the potassium titanate nanobelt material (reference of different-shape composition：Sung-Oong Kang,Hoon-Sik Jang,Yong-Il
Kim, Ki-Bok Kim, Maeng-Joon Jung, Study on the growth of potassium titanate
Nanostructures prepared by sol-gel-calcination process [J], Materials Letters,
2007,61：473–477).However, the technology is usually using expensive high-purity compound, and it is longer to react manufacturing cycle,
Products therefrom yield is low, only gram grade scale, is unsatisfactory for project scaleization at all and prepares requirement.Moreover, traditional scale system
In addition to high cost of material and preparation energy consumption are larger, another main problem is how to prepare shape standby crystal whisker of hexa potassium titanate
Looks are controllable, are applicable in the serial powder crystal material in different application field.For example, crystal whisker of hexa potassium titanate is as manufacture automotive friction brake block
Important reinforcing material requirement it is good dispersibility and suitable draw ratio, and be used as lithium ion battery separator material main component
High-performance crystal whisker materials then need to meet necessary intensity and thermal stability (reference：Xinxin Zhao,Zonglin
Zhang, Sisi Yang, Guangchuan Liang, Inorganic ceramic fiber separator for
electrochemical and safety performance improvement of lithium-ion batteries
[J], Ceramics International, 2017,43：14775–14783).Further, since traditional natural mineral fiber makes
With the discovery of the environment pathogenic mechanism of initiation, strengthen in the world and inhalable artificial nano whisker class material limitation is used
(reference：Roser Costa, Ramon Orriols, Man-Made Mineral Fibers and the Respiratory
Tract [J], Arch Bronconeumol.2012,48 (12):460–468).
Invention content
In order to solve the above technical problem, the present invention provides a kind of morphology controllable potassium hexatitanate powder crystal material and its low energy consumption
Preparation method.
In order to achieve the object of the present invention, present invention employs following technical schemes：
A kind of low energy consumption preparation method of morphology controllable potassium hexatitanate powder crystal material, includes the following steps：
Step 1, nano-anatase TiO2The preparation of powder：
Under stirring, titanium precursor will be contained to be slowly added in lower alcohol, and be then rapidly added deionized water and divided
Powder forms uniform faint yellow colloidal sol, and propylene oxide (PO) is slowly added into the colloidal sol after 13~17min strengthens promotion
Gelation reaction, after the gel of generation is placed 2 days under room temperature and ventilation condition, dry 5 under the conditions of 60~70 DEG C~
12h is sintered 1.5~2.5h under the conditions of 430~470 DEG C, obtains nano-anatase TiO after drying2Powder；
The titanium precursor that contains is TiCl3Or TiCl4Hydrochloric acid solution；The lower alcohol is absolute ethyl alcohol, isopropanol, positive fourth
Any one of alcohol is several；The volume ratio containing titanium precursor and lower alcohol is 1:(10~40), it is described to contain titanium precursor
Middle Ti elements, deionized water, the stoichiometric ratio of propylene oxide are 1:(1~3):(6~20)；
Step 2, potassium hexatitanate powder crystal material preparation：
The TiO that will be prepared2Powder is mixed and added into deionized water with potassium-containing compound and is configured to mixed liquor, and stirring surpasses
Moisture is dried and removed after sound mixed processing and obtains mixed-powder, the mixed-powder is heated up later calcine and select 700~
0.5~1h is kept the temperature under 850 DEG C of temperature conditions, the product obtained after calcining is washed, filtered, is dry by subsequent cooled to room temperature
Potassium hexatitanate powder crystal material is made afterwards；
The potassium-containing compound is potassium acetate, potassium acetate, potassium carbonate, saleratus, any one of potassium chloride or several,
The TiO2Both Ti elements and the K element in potassium-containing compound stoichiometric ratio are (2.5~3.5) in powder:1.
Further, dispersant is polyacrylic acid in the step 1, and the addition of the dispersant is the colloidal sol gross mass
0.1~0.5%.
Further, in the step 2 drying temperature of mixed liquor for 90~105 DEG C, drying time 5 of the mixed liquor~
6h。
Further, mixed-powder calcining heating rate is 2~5 DEG C/min in the step 2.
What a kind of preparation method prepared has the potassium hexatitanate of sheet, crystal whisker-shaped or the two mixing appearance structure
Powder crystal material.
The beneficial effects of the present invention are：
(1) the present invention provides a kind of substep and use it is cheap containing titanium halide for raw material, driven using propylene oxide
The pre- obtained high-activity nano Detitanium-ore-type TiO of sol-gel technique2Powder, synthesizing serial pattern using cryogenic calcining process can
The potassium hexatitanate powder crystal material of control.The present invention clear superiority be：Using cheap raw material, potassium titanate powder crystal material is significantly reduced
The temperature of synthesis has cost-effective, energy-saving meaning.Pass through preferred content of organics, K/Ti raw material proportionings, calcining temperature
Degree can prepare be evenly distributed, the serial morphology controllable potassium hexatitanate powder crystal material that draw ratio is high.Six titaniums that the present invention prepares
Sour potassium powder crystal material is sheet, crystal whisker-shaped or the two mix appearance structure, and whisker average diameter is at 0.2~0.5 μm, draw ratio
(L/D) maximum can reach 12, even thickness, favorable dispersibility.The potassium hexatitanate powder crystal material crystalline is good, morphology controllable,
Yield is high, widely used.
(2) present invention is driven using propylene oxide (PO), and ring-opening reaction, which occurs, with reaction dissolvent by epoxide catches
It obtains proton and fixes conjugate base so that pH value of solution is uniformly slowly increased to 7~8, accelerates the hydrolysis condensation reaction of titanium-containing compound, promotees
Into sol gel dynamic process, the reaction time of sol gel is reduced, the reaction time is within 15min.The present invention
Make Detitanium-ore-type TiO by oneself2Powder has the characteristics that ultra-fine and high activity, compared to the business nano-TiO of purchase2Raw material, the present invention can
The temperature of potassium titanate powder crystal materials synthesis reaction is greatly lowered.Synthetic method of the present invention is simple, easy to operate, reaction condition temperature
With contamination-free discharge.
(3) it should be strongly noted that by raw material composition and ratio, calcination temperature and the calcining in this preparation method
The control and cooperation of three kinds of factors of time, you can obtain the potassium hexatitanate of specific morphology and structure, this specific pattern and
Structure can be individual sheet-like morphology structure or individual whisker-like oxides structure, can also be have concurrently sheet and
The mixing appearance structure of crystal whisker-shaped.Change any one of above-mentioned three kinds of factors factor, may all make the shape of potassium hexatitanate
Looks and structure also change.However, anyway, the technical solution in the present invention, which takes the lead in realizing and ensure, can obtain shape
The controllable potassium hexatitanate powder crystal material of looks.
Description of the drawings
Fig. 1 is the nano-anatase TiO prepared in embodiment2X-ray diffractogram；
Fig. 2 is that embodiment 1,2,3 calcines the potassium hexatitanate material X-ray diffractogram that 0.5h is obtained；
Fig. 3 is that embodiment 1,2,3 calcines the potassium hexatitanate material X-ray diffractogram that 1h is obtained；
Fig. 4 is that embodiment 1 calcines the crystal whisker of hexa potassium titanate scanning electron microscope diagram that 0.5h is obtained；
Fig. 5 is that embodiment 1 calcines the potassium hexatitanate platelet scanning electron microscope diagram that 1h is obtained；
Fig. 6 is that embodiment 2 calcines the crystal whisker of hexa potassium titanate scanning electron microscope diagram that 0.5h is obtained；
Fig. 7 is that embodiment 2 calcines the potassium hexatitanate platelet scanning electron microscope diagram that 1h is obtained；
Fig. 8 is that embodiment 3 calcines potassium hexatitanate platelet, whisker mixed sweep electronic display that 0.5h is obtained
Micro mirror figure；
Fig. 9 is that embodiment 3 calcines the potassium hexatitanate platelet scanning electron microscope diagram that 1h is obtained.
Specific embodiment
More specific detail is made to technical solution of the present invention with reference to embodiment：
Embodiment 1：
Step 1, nano-anatase TiO2The preparation of powder
Presoma titanium tetrachloride presses V (TiCl4):V (absolute ethyl alcohol)=1:10 measure, under magnetic stirrer effect
By TiCl4It is slowly dropped in absolute ethyl alcohol, being rapidly added appropriate amount of deionized water and PAA, (PAA accounts for colloidal sol gross mass
0.1%) uniform faint yellow colloidal sol, is formed, propylene oxide (PO) is added dropwise after 13min, gelation reaction occurs immediately, molten
TiCl in colloid system4, deionized water, propylene oxide proportions n (Ti) in molar ratio：n(H2O)：N (PO)=1:3:6 controls.
After the gel of generation is placed at room temperature for 2 days in ventilation, dry 5h at 70 DEG C, is then ground to powder and is placed in porcelain in air dry oven
It is put into matter crucible in Muffle furnace and calcines 2h at 450 DEG C, obtained powder i.e. Anatase TiO2, XRD object phase compositions are shown in figure
1。
Why by TiCl4It is slowly dropped in absolute ethyl alcohol, is to make to be added drop-wise to the TiCl in absolute ethyl alcohol4It can
It is sufficiently uniformly mixed as far as possible with absolute ethyl alcohol.Therefore, TiCl4Rate of addition there is no specific limitation, be added dropwise
As long as slow degree makes TiCl4It can be equably sufficiently mixed with absolute ethyl alcohol.For example, TiCl4Rate of addition can
Think 10ml/min.
The preparation of step 2, potassium hexatitanate platelet
Nano-anatase TiO2 powder obtained is pressed into n (Ti)：N (K)=3:1 mixes with potassium acetate, add in 10ml go from
Sub- water is configured to mixed liquor, and stirring, ultrasound 30min are in favor of TiO2With being sufficiently mixed for potassium acetate, it is put into after being sufficiently mixed dry
In dry case mixed-powder is obtained in 90 DEG C of dry 6h moisture removed in mixture.Several mixed-powders are respectively put into 30ml high
0.5h at 750 DEG C is calcined using a step temperature-raising method respectively with Muffle furnace in aluminium crucible and obtains sample 1, calcining 1h obtains sample 2,
Cool to room temperature with the furnace.The crystal whisker of hexa potassium titanate and platelet that obtained product is obtained after washing, filtering, dry, XRD
Material phase analysis see Fig. 2,3 and pattern see Fig. 4,5.
Embodiment 2：
Step 1, nano-anatase TiO2The preparation of powder
Presoma titanium tetrachloride presses V (TiCl4)：V (absolute ethyl alcohol)=1:40 measure, under magnetic stirrer effect
By TiCl4It is slowly dropped in absolute ethyl alcohol, being rapidly added appropriate amount of deionized water and PAA, (PAA accounts for colloidal sol gross mass
0.3%) uniform faint yellow colloidal sol, is formed, n (Ti) is pressed after 15min：n(H2O)：N (PO)=1:1:12 are added dropwise epoxy third
Alkane (PO), gelation reaction occurs immediately, after the gel of generation is placed at room temperature for 2 days in ventilation, 60 DEG C in air dry oven
Lower dry 12h is then ground to powder and is placed in vitrified pot to be put into Muffle furnace be sintered 2.5h at 430 DEG C, and obtained powder is i.e.
Anatase TiO2, XRD is shown in Fig. 1.
The preparation of step 2, crystal whisker of hexa potassium titanate
By nano-anatase TiO obtained2Powder presses n (Ti)：N (K)=2.5:1 mixes with potassium acetate, adds in 10ml and goes
Ionized water is configured to mixed liquor, and stirring, ultrasound 30min are in favor of TiO2With being sufficiently mixed for potassium acetate, it is put into after being sufficiently mixed
In drying box mixed-powder is obtained in 90 DEG C of dry 6h moisture removed in mixture.Mixed-powder is put into 30ml high alumina crucibles
It is heated up at 800 DEG C using a step with Muffle furnace and calcines 0.5h respectively and obtain sample 1, calcining 1h obtains sample 2, furnace cooling
To room temperature.The crystal whisker of hexa potassium titanate and platelet that obtained product is obtained after washing, filtering, dry.Its XRD is shown in Fig. 2,3,
Pattern is shown in Fig. 6,7.
Embodiment 3：
Step 1, nano-anatase TiO2The preparation of powder
Presoma titanium tetrachloride presses V (TiCl4)：V (absolute ethyl alcohol)=1:20 measure, under magnetic stirrer effect
By TiCl4It is slowly dropped in absolute ethyl alcohol, being rapidly added appropriate amount of deionized water and PAA, (PAA accounts for colloidal sol gross mass
0.5%) uniform faint yellow colloidal sol, is formed, n (Ti) is pressed after 17min：n(H2O)：N (PO)=1:2:20 are added dropwise epoxy third
Alkane (PO), gelation reaction occurs immediately, after the gel of generation is placed at room temperature for 2 days in ventilation, 65 DEG C in air dry oven
Lower dry 8h is then ground to powder and is placed in vitrified pot to be put into Muffle furnace be sintered 1.5h at 470 DEG C, and obtained powder is i.e. sharp
Titanium ore phase TiO2, XRD is shown in Fig. 1.
The preparation of step 2, crystal whisker of hexa potassium titanate
By nano-anatase TiO obtained2Powder presses n (Ti)：N (K)=3.5:1 mixes with potassium acetate, adds in 10ml and goes
Ionized water is configured to mixed liquor, and stirring, ultrasound 30min are in favor of TiO2With being sufficiently mixed for potassium acetate, it is put into after being sufficiently mixed
In drying box mixed-powder is obtained in 105 DEG C of dry 5h moisture removed in mixture.Mixed-powder is put into 30ml high alumina crucibles
Middle to obtain sample 1 using a step at the 850 DEG C and respectively calcining 0.5h that heats up with Muffle furnace, calcining 1h obtains sample 2, with furnace cooling
But to room temperature.The crystal whisker of hexa potassium titanate and platelet that obtained product is obtained after washing, filtering, dry.Its XRD see Fig. 2,
3, pattern is shown in Fig. 8,9.
As shown in Fig. 4~Fig. 9：The pattern and structure of potassium hexatitanate of the present invention can be according to the originals described in preparation method
Composition and ratio, calcination temperature and calcination time are expected to control, i.e. technical solution of the present invention guarantee can obtain morphology controllable
Potassium hexatitanate powder crystal material.
Above example is only the section Example of the present invention, and potassium-containing compound is utilized according to preparation method of the present invention
For example the potassium hexatitanate powder crystal material of morphology controllable can be equally prepared in potassium nitrate, potassium carbonate, saleratus, potassium chloride.
Claims (5)
1. a kind of low energy consumption preparation method of morphology controllable potassium hexatitanate powder crystal material, it is characterised in that include the following steps：
Step 1, nano-anatase TiO2The preparation of powder：
Under stirring, titanium precursor will be contained to be slowly added in lower alcohol, and will then be rapidly added deionized water and dispersant
Uniform faint yellow colloidal sol is formed, propylene oxide is slowly added to after 13~17min into the colloidal sol and promotes generation gelation anti-
Should, after the gel of generation is placed 2 days under room temperature and ventilation condition, dry 5~12h under the conditions of 60~70 DEG C, dry knot
1.5~2.5h is sintered after beam under the conditions of 430~470 DEG C, obtains nano-anatase TiO2Powder；
The titanium precursor that contains is TiCl3Or TiCl4Hydrochloric acid solution；The lower alcohol is absolute ethyl alcohol, in isopropanol, n-butanol
It is any one or several；The volume ratio containing titanium precursor and lower alcohol is 1:(10~40), it is described containing Ti in titanium precursor
Element, deionized water, the stoichiometric ratio of propylene oxide are 1:(1~3):(6~20)；
Step 2, potassium hexatitanate powder crystal material preparation：
The TiO that will be prepared2Powder is mixed and added into deionized water with potassium-containing compound and is configured to mixed liquor, stirring, ultrasonic mixing
Moisture is dried and removed after processing and obtains mixed-powder, the mixed-powder heats up later and calcines and selects in 700~850 DEG C of temperature
0.5~1h is kept the temperature under the conditions of degree, the product obtained after calcining is washed, filters, is made after drying by subsequent cooled to room temperature
Potassium hexatitanate powder crystal material；
The potassium-containing compound is potassium acetate, potassium nitrate, potassium carbonate, saleratus, any one of potassium chloride or several, described
TiO2Both Ti elements and the K element in potassium-containing compound stoichiometric ratio are (2.5~3.5) in powder:1.
2. the low energy consumption preparation method of morphology controllable potassium hexatitanate powder crystal material as described in claim 1, it is characterised in that：Institute
It is polyacrylic acid to state dispersant in step 1, and the addition of the dispersant is the 0.1~0.5% of the colloidal sol gross mass.
3. the low energy consumption preparation method of morphology controllable potassium hexatitanate powder crystal material as described in claim 1, it is characterised in that：Institute
The drying temperature for stating mixed liquor in step 2 is 90~105 DEG C, 5~6h of drying time of the mixed liquor.
4. the low energy consumption preparation method of morphology controllable potassium hexatitanate powder crystal material as described in claim 1, it is characterised in that：Institute
It is 2~5 DEG C/min to state mixed-powder calcining heating rate in step 2.
5. any one of a kind of sheet prepared by any one of Claims 1 to 4 preparation method, crystal whisker-shaped or two
The potassium hexatitanate powder crystal material of kind shape characteristic mixing.
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