CN106944056A - A kind of preparation method of hollow ball sections titanium composite oxide - Google Patents
A kind of preparation method of hollow ball sections titanium composite oxide Download PDFInfo
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- CN106944056A CN106944056A CN201710173170.3A CN201710173170A CN106944056A CN 106944056 A CN106944056 A CN 106944056A CN 201710173170 A CN201710173170 A CN 201710173170A CN 106944056 A CN106944056 A CN 106944056A
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- tio
- hollow ball
- feo
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- hollow
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- 239000010936 titanium Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 title claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910015189 FeOx Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000001802 infusion Methods 0.000 claims abstract 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims abstract 2
- 150000003608 titanium Chemical class 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 7
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of hollow ball sections titanium composite oxide（FeOx/TiO2）Preparation method.With Ti (SO4)2, resorcinol and formaldehyde be raw material, through hydro-thermal, it is still aging, centrifuge, washing, dry, roasting obtains TiO2Hollow ball.Using infusion process, ferriferous oxide is loaded into titanium dioxide hollow ball surface, the parameter such as mole ratio, heating-up temperature, time by controlling molysite and titanium salt has been prepared into the regulatable hollow ball-type FeO of the Nomenclature Composition and Structure of Complexesx/TiO。
Description
Technical field
The present invention relates to a kind of hollow ball sections titanium composite oxide（FeOx/TiO2）Preparation method, belong to novel environmental
Technical field of function materials.
Background technology
In recent years, ferrotitanium composite oxides thing is widely used in field of environment pollution control.There are some researches show with specific group
There is the reactivity of catalytic degradation chlorinated aromatic hydrocarbons into the ferrotitanium composite oxides thing with structure.In addition people are it has also been found that ferrotitanium is compound
Oxide can be used as the functional material of SCR denitration, and such material shows high activity, N within the scope of wider temperature2Generation
Selective and anti-H2O, anti-SO2Poisoning performance.
With continuing to develop for material synthesis technology, environment functional material of many with hollow structure is prepared out,
And applied to the purification techniques of environmental contaminants.Compared with medicine ball, hollow ball has that density is low, specific surface area big, surface
The advantage of good penetrability, by changing the composition structure of hollow ball material, can be achieved the regulation and control of performance such as adsorb it, be catalyzed.
The preparation method of hollow ball is divided into hard template method, soft template method and template-free method, and the hollow ball that wherein prepared by hard template method is more
Uniform rule, but conventional hard template method need to first prepare template, then prepare hollow material, has that technical process is numerous and diverse to be lacked
Point.
In summary, ferrotitanium composite oxides thing can be used for the purification techniques of environmental contaminants, the ferrotitanium with hollow structure
Composite oxides are expected to obtain more superior purifying property because of the advantage of its Nomenclature Composition and Structure of Complexes.However, but up to the present,
Still lack the short-cut method of ferrotitanium composite oxides thing of the synthesis with hollow structure.
The present invention, using one-step synthesis, is prepared for a kind of hollow ball-type FeO aiming above mentioned problemx/TiO2Material.
The content of the invention
The present invention provides one kind and prepares hollow ball-type FeOx/TiO2The method of material.
（1）TiO2The preparation of hollow ball：
Weigh a certain amount of Ti (SO4)2With resorcinol in beaker, deionized water is added, stirring is clarified completely until solution,
Wherein Ti (SO4)2Mass ratio with resorcinol is 0.5:1-5:1；Then the formalin of measured amounts（35 wt%）In play
It is quickly adding under strong stirring condition in above-mentioned mixed liquor, wherein the mass ratio of resorcinol and formaldehyde is 0.1:1-3:1, stirring
It is transferred to after several minutes in reactor, in an oven 60-120 °C of isothermal reaction 12-48 h.Take out, be cooled to after the completion of reaction
Room temperature, TiO is obtained through still aging, centrifugation, washing, dry, roasting2Hollow ball.
（2）Hollow ball-type FeOx/TiO2The preparation of material：
With TiO2Hollow ball is carrier, loads the ferriferous oxide of different proportion, concretely comprises the following steps：Weigh the Fe of certain mass
(NO3)3·9H2O, adds deionized water, and stirring is clarified completely until solution, weighs a certain amount of TiO2Hollow ball, is added to above-mentioned
Fe(NO3)3In solution, 0.2-1 h are stirred, water is evaporated, hollow ball-type FeO is obtained after obtained sample is firedx/TiO2Material
Material.
After the research report discussed in background technology is compared relatively with the technology of the present invention content, it can be seen that the present invention and the back of the body
Scape technology differ part be：The FeO preparedx/TiO2Material has hollow structure.
Embodiment
To be best understood from present disclosure, below by embodiment, the present invention is further illustrated, but lifts it
Example is not intended to limit protection scope of the present invention.
Embodiment 1：
First, 6.0 gTi (SO are weighed4)2It is dissolved in 4.0 g resorcinols in 40 mL deionized waters, 15min is to complete for stirring
Fully dissolved, then measures 5.6 mL formalins（35 wt%）, it is quickly adding under intense agitation in above-mentioned mixed liquor.
It is transferred to after stirring 5 min in reactor, in an oven 75 DEG C of h of isothermal reaction 48.Taken out after the completion of reaction, be cooled to room temperature,
With deionized water eccentric cleaning for several times, 75 DEG C of dried overnights.Last 450 DEG C of 2 h of roasting of desciccate, are made TiO2Hollow ball.
Weigh the Fe (NO of respective quality3)3·9H2O（Analysis is pure）Solid, adds 25 mL distilled water, stirs to be formed
Corresponding Fe (NO3)3Solution.Weigh TiO after 200 mg drying2Product adds the Fe (NO prepared to 25 mL3)3·9H2O is molten
Liquid, 0.5 h is stirred by above-mentioned suspension, and then room temperature places 48 h, and water is evaporated by 150 DEG C of 5 h of drying afterwards, by the sample being evaporated
400 DEG C of 3 h of calcining of product.The amount of Fe material is 5% after load（Fe/(Fe+Ti)）FeOx/TiO2Material, labeled as TiFe5.
Embodiment 2：
First, 6.0 gTi (SO are weighed4)2It is dissolved in 4.0 g resorcinols in 40 mL deionized waters, 15min is to complete for stirring
Fully dissolved, then measures 6.5 mL formalins（35 wt%）, it is quickly adding under intense agitation in above-mentioned mixed liquor.
It is transferred to after stirring 10 min in reactor, in an oven 75 DEG C of h of isothermal reaction 48.Taken out after the completion of reaction, be cooled to room
Temperature, with deionized water eccentric cleaning for several times, 75 DEG C of dried overnights.Last 450 DEG C of 2 h of roasting of desciccate, are made TiO2It is hollow
Ball.
Weigh the Fe (NO of respective quality3)3·9H2O（Analysis is pure）Solid, adds 25 mL distilled water, stirs to be formed
Corresponding Fe (NO3)3Solution.Weigh TiO after 200 mg drying2Product adds the Fe (NO prepared to 25 mL3)3·9H2O is molten
Liquid, 0.5 h is stirred by above-mentioned suspension, and then room temperature places 48 h, and water is evaporated by 150 DEG C of 5 h of drying afterwards, by the sample being evaporated
450 DEG C of 2 h of calcining of product.The amount of Fe material is 10% after load（Fe/(Fe+Ti)）FeOx/TiO2Material, is labeled as
TiFe10。
Embodiment 3：
First, 6.0 gTi (SO are weighed4)2It is dissolved in 2.0 g resorcinols in 50 mL deionized waters, 20 min are to complete for stirring
Fully dissolved, then measures 8 mL formalins（35 wt%）, it is quickly adding under intense agitation in above-mentioned mixed liquor.Stir
It is transferred to after mixing 5 min in reactor, in an oven 75 DEG C of h of isothermal reaction 48.Taken out after the completion of reaction, be cooled to room temperature, used
Deionized water eccentric cleaning for several times, 75 DEG C of dried overnights.Last 500 DEG C of 2 h of roasting of desciccate, are made TiO2Hollow ball.
Weigh the Fe (NO of respective quality3)3·9H2O（Analysis is pure）Solid, adds 25 mL distilled water, stirs to be formed
Corresponding Fe (NO3)3Solution.Weigh TiO after 100 mg drying2Product adds the Fe (NO prepared to 15 mL3)3·9H2O is molten
Liquid, 1 h is stirred by above-mentioned suspension, and then room temperature places 48 h, and water is evaporated by 120 DEG C of 6 h of drying afterwards, by the sample being evaporated
450 DEG C of 2 h of calcining.The amount of Fe material is 15% after load（Fe/(Fe+Ti)）FeOx/TiO2Material, labeled as TiFe15.
Embodiment 4：
First, 6.0 gTi (SO are weighed4)2It is dissolved in 4.5 g resorcinols in 60 mL deionized waters, 30 min are to complete for stirring
Fully dissolved, then measures 7 mL formalins（35 wt%）, it is quickly adding under intense agitation in above-mentioned mixed liquor.Stir
It is transferred to after mixing 10 min in reactor, in an oven 75 DEG C of h of isothermal reaction 48.Taken out after the completion of reaction, be cooled to room temperature,
With deionized water eccentric cleaning for several times, 75 DEG C of dried overnights.Last 500 DEG C of 2 h of roasting of desciccate, are made TiO2Hollow ball.
Weigh the Fe (NO of respective quality3)3·9H2O（Analysis is pure）Solid, adds 25 mL distilled water, stirs to be formed
Corresponding Fe (NO3)3Solution.Weigh TiO after 200 mg drying2Product adds the Fe (NO prepared to 25 mL3)3·9H2O is molten
Liquid, 1 h is stirred by above-mentioned suspension, and then room temperature places 48 h, and water is evaporated by 120 DEG C of dry 6h afterwards, by the sample being evaporated
550 DEG C of 2 h of calcining.The amount of Fe material is 20% after load（Fe/(Fe+Ti)）FeOx/TiO2Material, labeled as TiFe20.
Claims (5)
1. a kind of hollow ball sections titanium composite oxide（FeOx/TiO2）Preparation method, it is characterised in that with Ti (SO4)2, isophthalic
Diphenol and formaldehyde are raw material, and TiO is prepared through Hydrothermal Synthesiss2Hollow ball carrier.Using infusion process, ferriferous oxide is loaded to
TiO2Hollow ball carrier surface, the parameter such as mole ratio, reaction temperature, time by controlling molysite and titanium salt, is prepared into
The regulatable hollow ball-type FeO of the Nomenclature Composition and Structure of Complexesx/TiO2Material.
2. a kind of hollow ball-type FeO as claimed in claim 1x/TiO2The preparation method of material, it is characterised in that Ti (SO4)2
Mass ratio with resorcinol is 0.5:1-5:1.
3. a kind of hollow ball-type FeO as claimed in claim 1x/TiO2The preparation method of material, it is characterised in that wherein isophthalic
The mass ratio of diphenol and formaldehyde is 0.1:1-3:1.
4. a kind of hollow ball-type FeO as claimed in claim 1x/TiO2The preparation method of material, it is characterised in that TiO2To carry
Body, and with hollow structure.
5. a kind of hollow ball-type FeO as claimed in claim 1x/TiO2The preparation method of material, it is characterised in that with hollow
The TiO of structure2Carrier surface has loaded FeOx。
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| CN201710173170.3A CN106944056B (en) | 2017-03-22 | 2017-03-22 | A kind of preparation method of hollow ball sections titanium composite oxide |
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| CN201710173170.3A CN106944056B (en) | 2017-03-22 | 2017-03-22 | A kind of preparation method of hollow ball sections titanium composite oxide |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428220A (en) * | 2008-12-26 | 2009-05-13 | 北京化工大学 | Magnetic titanium dioxide hollow ball and preparation method thereof |
| CN101890350A (en) * | 2010-07-21 | 2010-11-24 | 江苏大学 | Method for preparing Fe3+doped TiO2 hollow sphere catalyst and application thereof |
| CN102382706A (en) * | 2011-08-30 | 2012-03-21 | 华北电力大学 | Cavity structure TiO2 based Fe-based oxygen carrier and its preparation method |
| CN103861598A (en) * | 2012-12-17 | 2014-06-18 | 南开大学 | Preparation of calcium-doped iron oxide hollow sphere and application of hollow sphere to catalytically oxidize chloro-substituted volatile organic compounds |
| CN106111186A (en) * | 2016-06-28 | 2016-11-16 | 陈建峰 | A kind of preparation method of hollow structure multistage pore canal TS 1 molecular sieve |
-
2017
- 2017-03-22 CN CN201710173170.3A patent/CN106944056B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428220A (en) * | 2008-12-26 | 2009-05-13 | 北京化工大学 | Magnetic titanium dioxide hollow ball and preparation method thereof |
| CN101890350A (en) * | 2010-07-21 | 2010-11-24 | 江苏大学 | Method for preparing Fe3+doped TiO2 hollow sphere catalyst and application thereof |
| CN102382706A (en) * | 2011-08-30 | 2012-03-21 | 华北电力大学 | Cavity structure TiO2 based Fe-based oxygen carrier and its preparation method |
| CN103861598A (en) * | 2012-12-17 | 2014-06-18 | 南开大学 | Preparation of calcium-doped iron oxide hollow sphere and application of hollow sphere to catalytically oxidize chloro-substituted volatile organic compounds |
| CN106111186A (en) * | 2016-06-28 | 2016-11-16 | 陈建峰 | A kind of preparation method of hollow structure multistage pore canal TS 1 molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| 王萌: "碳球与SnO2空心球的制备及其电化学性能研究", 《中国学位论文全文数据库》 * |
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