CN104176771A - Preparation method and application of superlong titanic acid micro/nano tubes - Google Patents
Preparation method and application of superlong titanic acid micro/nano tubes Download PDFInfo
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- CN104176771A CN104176771A CN201410398714.2A CN201410398714A CN104176771A CN 104176771 A CN104176771 A CN 104176771A CN 201410398714 A CN201410398714 A CN 201410398714A CN 104176771 A CN104176771 A CN 104176771A
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- metatitanic acid
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Abstract
The invention belongs to the field of titanic acid micro/nano tubes, particularly relates to a preparation method and application of superlong titanic acid micro/nano tubes, and further relates to superlong titanic acid micro/nano tubes prepared by the method. The preparation method comprises the following steps: proportionally and uniformly stirring TiO2 powder and a NaOH water solution; transferring the obtained mixed suspension into a high-pressure autoclave, and carrying out hydrothermal reaction at 100-200 DEG C; carrying out solid-liquid separation on the obtained reaction product, and washing the solid phase to a neutral state; and immersing the product in a hydrochloric acid or nitric acid water solution, carrying out solid-liquid separation, and drying to obtain the titanic acid micro/nano tubes. The method has the advantages of simple equipment, low cost, environment friendliness and no pollution, can easily implement large-scale production, greatly enhances the washing efficiency, and provides possibilities for large-scale industrial production.
Description
Technical field
The present invention relates to metatitanic acid micro-nano mitron field, particularly relate to the preparation method and its usage of the micro-nano pipe of a kind of overlength metatitanic acid, and further relate to the prepared metatitanic acid micro-nano mitron of preparation method of the micro-nano pipe of described overlength metatitanic acid.
Background technology
Nano titanium oxide is present in variform, and wherein nanotube receives much concern because it has compared with bigger serface and stronger adsorptive power.The method of preparing at present titania nanotube mainly contains sol-gel method, hydrothermal method, template and anonizing.Wherein, the synthetic nanotube size of template depends on the size and dimension of template, is difficult to the synthetic small-bore nanotube of small size, complete processing difficulty simultaneously, and follow-up work complexity is lengthy and tedious, is difficult to realize extensive preparation; The caliber that anonizing generally prepares is larger, and pipe range is short, and secondly gained nanotube is generally single-ended opening.And the made nanotube uniform diameter of hydrothermal method, productive rate is high, simultaneously simple to operate, with low cost, is to be expected to be applied to industrial preparation method most.1998, Kasuga etc. reported that preparation process is by TiO about the initiative work of the synthetic titanate radical nanopipe of hydrothermal method
2powder and NaOH solution mix and carry out at a certain temperature hydrothermal treatment consists, and the caliber of the nanotube of acquisition is about 10nm left and right, and specific surface area is about 400m
2g
-1.
Publication number is that the patent of CN103693681A is used hydrothermal synthesis method to prepare super-long titanium hydrochlorate micro-nano mitron.The metatitanic acid micro-nano mitron that it is prepared, length is at 1 μ m～10 μ m, and diameter is about 10-30nm, and length-to-diameter ratio (length/diameter) is 33.3～1000.Overlength nanotube good dispersity, and can mix with the cellulose acetate in cigarette filter crosslinkedly, solve to a certain extent the nano-powder adding in cigarette filter and be inhaled into because coming off the problem of human body.The sorbing material of this patent in further using super-long titanium hydrochlorate micro-nano mitron as cigarette filter, experimental result shows that it can effectively reduce that cigarette mainstream flue gas is coal-tar middle oil, the burst size of carbon monoxide and ammonia.
In order to meet actual production demand, in particularly scale production process, material preparation generally should be made every effort to aftertreatment simple and fast to ensure higher production efficiency.Publication number is the preparation method who uses in the patent of CN103693681A, product after washing water thermal response is to neutral process, because a large amount of negative charges of product band form stable emulsion, in suction filtration process, easily stop up sand core funnel and cause expending plenty of time and the energy.The present invention adopts simple method to comprise can destroy the emulsion that mutually repels generation because of static with hot sodium chloride solution, do not affecting under the prerequisite of final titanate nanotube form, greatly improve post-reaction treatment efficiency, can be scale operation overlength titanate nanotube effective approach is provided.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide the preparation method and its usage of the micro-nano pipe of a kind of overlength metatitanic acid, for solving the problems of the prior art.
For achieving the above object and other relevant objects, first aspect present invention provides the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid, the present invention is taking nano titanium oxide as raw material, in highly basic medium, carry out hydro-thermal reaction, the solid that solid-liquid separation obtains afterwards, again be soaked in acidifying in hydrochloric acid or aqueous nitric acid and obtain the micro-nano titanate of tubulose, specifically comprise the steps:
(1) by TiO
2powder mixes by a certain percentage with the NaOH aqueous solution, obtains relatively stable suspension liquid, described NaOH and TiO
2mol ratio be 20～100:1;
(2) mixing suspension liquid step (1) being obtained moves in autoclave, airtight, at the temperature of 100～200 DEG C, stirs and carries out hydro-thermal reaction;
(3), by step (2) gained reaction product solid-liquid separation, solid phase washing is to neutral;
(4) step (3) products therefrom is soaked in hydrochloric acid or aqueous nitric acid, solid-liquid separation, oven dry, obtain described metatitanic acid micro-nano mitron.
Preferably, in described step (1), the concentration of the NaOH aqueous solution is 9.6-10.4M.
Preferably, in described step (1), described NaOH and TiO
2mol ratio be 38-42:1.
Described NaOH and TiO
2mol ratio specifically refer to NaOH contained in the aqueous solution and TiO
2mol ratio.
Preferably, in described step (2), the time of hydro-thermal reaction is 12～36h.
When hydro-thermal reaction, those skilled in the art can rule of thumb, adjust the amount of reaction solution in autoclave, and reaction solution is carried out to agitation as appropriate.Generally, the volume of reaction solution accounts for 50%～80% of autoclave volume, and stirring velocity is 200～500r/min.
Preferably, in described step (3), use distilled water or the NaCl aqueous solution that solid phase washing is extremely neutral.
Preferred, in described step (3), use the NaCl aqueous solution that solid phase washing is extremely neutral, NaCl can be room temperature, further preferred, the temperature of the NaCl aqueous solution is 65-75 DEG C.
In whole preparation process, can use the various routine techniquess in this area to carry out solid-liquid separation, in step (3), preferred solid-liquid separation method is suction filtration or centrifugal, in step (4), preferred solid-liquid separation method is suction filtration.
Preferred, the mass percent concentration of the described NaCl aqueous solution is 4.5-5.5%.
Preferably, in described step (4), the pH value of hydrochloric acid or aqueous nitric acid is 0.01～3, and the time span of immersion is 12～36h.
Preferred, in described step (4), the pH value of hydrochloric acid or aqueous nitric acid is 0.9-1.1.
Second aspect present invention provides the preparation method of the micro-nano pipe of described overlength metatitanic acid in the purposes of the micro-nano pipe preparation field of metatitanic acid.
Third aspect present invention provides the overlength metatitanic acid micro-nano pipe prepared by the preparation method of the micro-nano pipe of described overlength metatitanic acid.
Preferably, the length of the micro-nano pipe of described overlength metatitanic acid is 1 μ m-10 μ m.
As mentioned above, the preparation method of the micro-nano pipe of overlength metatitanic acid provided by the present invention, is taking titanium dioxide and sodium hydroxide as raw material, adopts low temperature to stir hydro-thermal reaction, with the hot NaCl aqueous solution, by product, washing is extremely neutral fast afterwards, then soaks and obtain titanate nanotube with acid solution.Compared with prior art, the present invention has following beneficial effect:
(1) the present invention prepares the method for the micro-nano pipe of overlength metatitanic acid, in reaction process, without adding other additive, does not need complicated processing can obtain the micro-nano pipe of overlength metatitanic acid of good dispersity.Equipment used is simple, and cost is low, is easy to large-scale production, and environmental protection is pollution-free.
(2) do not affecting under the prerequisite of titanate nanotube form; utilize the hot NaCl aqueous solution can destroy the emulsion because forming with a large amount of negative charges at hydro-thermal reaction after product; promote precipitation to form; effectively avoid sand core funnel latch up phenomenon; thereby greatly improve detersive efficiency, produce possibility is provided for large-scale industrial.
Brief description of the drawings
Fig. 1 is shown as the stereoscan photograph (5,000 times) of the metatitanic acid micro-nano mitron that the embodiment of the present invention 1 obtains;
Fig. 2 is shown as the stereoscan photograph (5,000 times) of the metatitanic acid micro-nano mitron that the embodiment of the present invention 2 obtains;
Fig. 3 is shown as the stereoscan photograph (5,000 times) of the metatitanic acid micro-nano mitron that the embodiment of the present invention 3 obtains;
Fig. 4 is shown as the stereoscan photograph (5,000 times) of the metatitanic acid micro-nano mitron that the embodiment of the present invention 4 obtains.
Embodiment
Below, by specific specific examples explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets.The present invention can also be implemented or be applied by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
Notice, processing unit or device concrete not dated in the following example all adopt conventional equipment or the device in this area; All force value and scope all refer to absolute pressure.
In addition should be understood that one or more method stepss of mentioning in the present invention do not repel between the step that can also have additive method step or clearly mention at these before and after described combination step can also insert additive method step, except as otherwise noted; Will also be understood that, the relation that is connected between one or more equipment/devices of mentioning in the present invention is not repelled between two equipment/devices that can also have other equipment/devices or clearly mention at these before and after described clustered aggregates/device can also insert other equipment/devices, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, in the situation that changing technology contents without essence, when being also considered as the enforceable category of the present invention.
The present invention utilizes the reactant of hot sodium chloride solution washing water thermal response synthesized, shortens finishing time, improves efficiency of post treatment, for the micro-nano pipe of large-scale production overlength metatitanic acid provides basis.The method solvent for use is simple, and cost is low, and processes hydro-thermal reaction product with distilled water merely and compares, and the pattern of product, productive rate are several without impact, for the application of super-long titanium hydrochlorate micro-nano mitron in cigarette industry provides possibility.
Embodiment 1:
By 6.0g TiO
2(0.075mol) being dissolved in 300mL concentration is in the 10M NaOH aqueous solution (containing 3mol NaOH), mixing solutions is moved into 500mL autoclave, put into subsequently oil bath pan, stirring velocity is 400r/min, hydrothermal treatment consists 24h at the temperature of 130 DEG C.After reaction finishes, suction filtration separated product, and extremely neutral with distilled water wash product, in the hydrochloric acid soln of pH=1, soak 24h subsequently, suction filtration, oven dry, finally obtain metatitanic acid micro-nano mitron.In the present embodiment, while carrying out suction filtration separation, owing to forming comparatively stable emulsion, cause sand core funnel seriously to stop up after hydrothermal synthesis reaction, washing time is long, and solvent load is large.
Embodiment 2:
By 6.0g TiO
2(0.075mol) being dissolved in 300mL concentration is in the 10M NaOH aqueous solution (containing 3mol NaOH), mixing solutions is moved into 500mL autoclave, put into subsequently oil bath pan, stirring velocity is 400r/min, hydrothermal treatment consists 24h at the temperature of 130 DEG C.After reaction finishes, centrifugation product, and extremely neutral with distilled water wash product, in the hydrochloric acid soln of pH=1, soak 24h subsequently, suction filtration, oven dry, finally obtain metatitanic acid micro-nano mitron.In the present embodiment, carry out centrifugation after hydrothermal synthesis reaction time, owing to forming comparatively stable emulsion, centrifugation time is long, and centrifugal settling is not thorough, and every batch processed amount is less.
Embodiment 3:
By 6.0g TiO
2(0.075mol) being dissolved in 300mL concentration is in the 10M NaOH aqueous solution (containing 3mol NaOH), mixing solutions is moved into 500mL autoclave, put into subsequently oil bath pan, stirring velocity is 400r/min, hydrothermal treatment consists 24h at the temperature of 130 DEG C.After reaction finishes, suction filtration separated product, and be that 5%NaCl solution washing product is extremely neutral by mass percent, in the hydrochloric acid soln of pH=1, soaking 24h subsequently, suction filtration, oven dry, finally obtain metatitanic acid micro-nano mitron.In the present embodiment, carry out suction filtration separation after hydrothermal synthesis reaction time, because NaCl solution can destroy emulsion, impel particles in solution sedimentation to assemble, reduce sand core funnel latch up phenomenon; Improve post-reaction treatment efficiency.
Embodiment 4:
By 6.0g TiO
2(0.075mol) being dissolved in 300mL concentration is in the 10M NaOH aqueous solution (containing 3mol NaOH), mixing solutions is moved into 500mL autoclave, put into subsequently oil bath pan, stirring velocity is 400r/min, hydrothermal treatment consists 24h at the temperature of 130 DEG C.After reaction finishes, suction filtration separated product, and be that 5%NaCl solution washing product is extremely neutral by 70 DEG C of mass percents, in the hydrochloric acid soln of pH=1, soaking 24h subsequently, suction filtration, oven dry, finally obtain metatitanic acid micro-nano mitron.In the present embodiment, carry out suction filtration separation after hydrothermal synthesis reaction time, because hot NaCl solution can effectively destroy emulsion, the rapid sedimentation of particles in solution is assembled, and greatly reduces sand core funnel latch up phenomenon; The solution of comparatively high temps is conducive to NaOH dissolving simultaneously, thereby improves to a great extent post-reaction treatment efficiency and reduce solvent load.
Performance test:
1. surface topography
Fig. 1 has shown scanning electron microscope (SEM) photo (magnification is 5,000 times) of embodiment 1 products therefrom, can find out metatitanic acid in tubular construction, favorable dispersity, and the length of gained metatitanic acid micro-nano mitron is about 1-10 μ m.
Scanning electron microscope (SEM) photo of embodiment 2 products therefroms is similar to embodiment 1.
Fig. 3 has shown scanning electron microscope (SEM) photo (magnification is 5,000 times) of embodiment 3 products therefroms, can find out metatitanic acid in tubular construction, favorable dispersity, and the length of gained metatitanic acid micro-nano mitron is about 1-10 μ m.
Scanning electron microscope (SEM) photo of embodiment 4 products therefroms is similar to embodiment 3.
Above-mentioned Electronic Speculum figure result shows that different post-treating method used is little on the form impact of titanate micro-nano mitron.
In sum, the present invention has effectively overcome various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, such as in affiliated technical field, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (11)
1. a preparation method for the micro-nano pipe of overlength metatitanic acid, specifically comprises the steps:
(1) by TiO
2powder and the NaOH aqueous solution are uniformly mixed by a certain percentage, obtain and stablize suspension liquid, described NaOH and TiO
2mol ratio be 20～100:1;
(2) mixing suspension liquid step (1) being obtained moves in autoclave, airtight, carries out hydro-thermal reaction at the temperature of 100～200 DEG C;
(3), by step (2) gained reaction product solid-liquid separation, solid phase washing is to neutral;
(4) step (3) products therefrom is soaked in hydrochloric acid or aqueous nitric acid, solid-liquid separation, oven dry, obtain described metatitanic acid micro-nano mitron.
2. the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid as claimed in claim 1, is characterized in that, in described step (1), the concentration of the NaOH aqueous solution is 9.6-10.4M.
3. the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid as claimed in claim 1, is characterized in that, in described step (1), and described NaOH and TiO
2mol ratio be 38-42:1.
4. the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid as claimed in claim 1, is characterized in that, in described step (2), the time of hydro-thermal reaction is 12～36h.
5. the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid as claimed in claim 1, is characterized in that, in described step (3), uses distilled water or the NaCl aqueous solution that solid phase washing is extremely neutral.
6. the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid as claimed in claim 5, is characterized in that, the temperature of the NaCl aqueous solution using in described step (3) is 65-75 DEG C.
7. the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid as claimed in claim 5, is characterized in that, the mass percent concentration of the described NaCl aqueous solution is 4.5-5.5%.
8. the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid as claimed in claim 1, is characterized in that, in described step (4), the time span that hydrochloric acid or aqueous nitric acid soak is 12～36h.
9. the preparation method of the micro-nano pipe of a kind of overlength metatitanic acid as claimed in claim 8, is characterized in that, in described step (4), the pH value of hydrochloric acid or aqueous nitric acid is 0.1-1.
10. the preparation method of the micro-nano pipe of overlength metatitanic acid as described in claim as arbitrary in claim 1-9 is in the purposes of the micro-nano pipe preparation field of metatitanic acid.
The prepared micro-nano pipe of overlength metatitanic acid of preparation method of the micro-nano pipe of overlength metatitanic acid as described in 11. claims as arbitrary in claim 1-9.
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| CN201410398714.2A CN104176771A (en) | 2014-08-13 | 2014-08-13 | Preparation method and application of superlong titanic acid micro/nano tubes |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974014A (en) * | 2016-10-21 | 2018-05-01 | 苏州今道创业投资有限公司 | A kind of preparation method of metatitanic acid micro-nano mitron/PVDF composite membranes |
| CN108315754A (en) * | 2018-02-12 | 2018-07-24 | 西南大学 | Preparation method based on transition metal ion-modified alkali metal titanate hydrogen-precipitating electrode |
| CN109174051A (en) * | 2018-08-28 | 2019-01-11 | 武汉理工大学 | A kind of preparation method protonating titanate nanotube and its adsorption applications to uranium, caesium |
| CN109926016A (en) * | 2019-04-04 | 2019-06-25 | 广州大学 | A kind of adsorbent material, preparation method and its application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693681A (en) * | 2013-12-11 | 2014-04-02 | 贵州中烟工业有限责任公司 | Method for preparing super-long titanate micro/nanotubes |
-
2014
- 2014-08-13 CN CN201410398714.2A patent/CN104176771A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693681A (en) * | 2013-12-11 | 2014-04-02 | 贵州中烟工业有限责任公司 | Method for preparing super-long titanate micro/nanotubes |
Non-Patent Citations (1)
| Title |
|---|
| 顾觉奋: "《分离纯化工艺原理》", 31 August 2002 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974014A (en) * | 2016-10-21 | 2018-05-01 | 苏州今道创业投资有限公司 | A kind of preparation method of metatitanic acid micro-nano mitron/PVDF composite membranes |
| CN108315754A (en) * | 2018-02-12 | 2018-07-24 | 西南大学 | Preparation method based on transition metal ion-modified alkali metal titanate hydrogen-precipitating electrode |
| CN108315754B (en) * | 2018-02-12 | 2020-05-26 | 西南大学 | Preparation method of transition metal ion modified alkali metal titanate based hydrogen evolution electrode |
| CN109174051A (en) * | 2018-08-28 | 2019-01-11 | 武汉理工大学 | A kind of preparation method protonating titanate nanotube and its adsorption applications to uranium, caesium |
| CN109926016A (en) * | 2019-04-04 | 2019-06-25 | 广州大学 | A kind of adsorbent material, preparation method and its application |
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