CN102154697A - Preparation method of TiO2 crystal whiskers and method for adsorbing metal ions by using TiO2 crystal whiskers - Google Patents
Preparation method of TiO2 crystal whiskers and method for adsorbing metal ions by using TiO2 crystal whiskers Download PDFInfo
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- CN102154697A CN102154697A CN 201110066392 CN201110066392A CN102154697A CN 102154697 A CN102154697 A CN 102154697A CN 201110066392 CN201110066392 CN 201110066392 CN 201110066392 A CN201110066392 A CN 201110066392A CN 102154697 A CN102154697 A CN 102154697A
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Abstract
The invention discloses a preparation method of TiO2 crystal whiskers, and relates to a preparation method of TiO2 crystal whiskers and a method for adsorbing metal ions such as copper ions, lead ions or chromium ions by using the TiO2 crystal whiskers. The preparation method comprises the following steps of: (1) adding metatitanic acid and trisodium citrate into distilled water, ultrasonically dispersing and fully mixing; (2) reacting at the temperature of 150 DEG C for 18 hours, adjusting the pH value to 7, adding 4-12 mol/L of KOH solution, ultrasonically dispersing for 6 hours, and stirring for 4 hours for fully mixing; and (3) reacting at the temperature of 100-150 DEG C for 24-96 hours, naturally cooling a reaction kettle to room temperature, performing suction filtration on a reactant, washing with deionized water until the electrical conductivity of the filtrate is less than 20 mS/m, and drying a filter cake at the temperature of 100 DEG C for 12 hours to obtain a product. In the preparation method, the TiO2 crystal whiskers are prepared by taking metatitanic acid with low cost as a raw material and KOH as a hydrothermal medium and are used for adsorbing heavy metals such as copper, lead and chromium.
Description
Technical field
The present invention relates to a kind of TiO
2The method of Preparation of Whiskers method and absorbing copper thereof, lead or chromium metal ion, refering in particular to the metatitanic acid is that reaction precursor body, KOH solution are the hydro-thermal medium, the method that adopts secondary Hydrothermal Preparation potassium titanate crystal whisker and copper, lead, chromium metal ion are adsorbed.
Background technology
Along with developing rapidly of industrial production and urban modernization, a large amount of heavy metal-containing waste waters enter water body, and environment is caused great harm.Heavy metal ion in the water body can not be at natural degradation under the physical environment, and often can enter animal and plant body by food chain, and then threatens human health.For example plumbous hemopoietic system, nervous tissue and the kidney that can invade the people, thus cause that neurasthenia, microcytic anemia and hypochrosis, cerebral lesion and ephrosis become; Excessive copper can cause hepatorenal damage; The chromium element can not only cause dermatitis, eczema, trachitis and rhinitis to the murder by poisoning of human body, and carcinogenesis is arranged.Therefore how handling heavy metal wastewater thereby is extremely urgent environmental problem.
The method of traditional processing heavy metal ion comprises chemical precipitation, ion-exchange, electrochemical treatment, reverse osmosis, membrane technique, distillation, electrodialysis etc., but these method ubiquity working cost height, clearance are lower, easily produce secondary pollution problems.Absorption method is as a kind of technology of emerging processing heavy metal wastewater thereby, and it is simple to have raw material sources, removes advantages such as efficient height, processing cost are low.
Summary of the invention
The objective of the invention is with metatitanic acid is former material precursor, at the interval preparation of certain alkaline concentration TiO
2Whisker, raw material are easy to obtain, and be with low cost, and the crystalline form of preparation is applied to the absorption removal of heavy metal ion such as copper-lead chromium.
Technical scheme of the present invention is as follows:
A kind of TiO
2The Preparation of Whiskers method, carry out according to following step: (1) adds distilled water with metatitanic acid and trisodium citrate, and regulating pH is 2, and ultra-sonic dispersion 6 h stir 4 h, reach thorough mixing.
(2) slurry that makes is moved in the autoclave, under 150 ℃, react 18 h reactor is naturally cooled to room temperature, regulating pH is 7, adds 4～12 mol/L KOH solution, and ultra-sonic dispersion 6 h stir 4 h, reach thorough mixing.
(3) slurry that makes is moved in the autoclave, under 100 ℃～150 ℃, reaction 24～96h naturally cools to room temperature with reactor; Reactant is filtered, uses deionized water wash, until the specific conductivity of filtrate less than 20 mS/m; Filtration cakes torrefaction is promptly got product, and drying temperature is 100 ℃, and be 12 h time of drying.
Wherein the main component in the metatitanic acid described in the step (1) is TiO
2, the TiO in the metatitanic acid
2Content is 36.03%; The add-on of trisodium citrate is TiO by quality ratio
21%～5%.
The contained TiO of metatitanic acid in the step (2) wherein
2With the quality and the volume ratio of KOH solution be 1～4:40 g/mL.
Above-mentioned TiO
2The method of whisker absorbing copper metal ion is carried out according to following step: the TiO that takes by weighing above-mentioned preparation
2Whisker joins in the solution of copper ions 20～200 mg/L, 5～40 ℃ of temperature of reaction, reaction times 150 min, wherein TiO
2The ratio of whisker and cupric ion is 0.015～1.5 mg/ mg.
Above-mentioned TiO
2Whisker absorption lead metal ionic method is carried out according to following step: the TiO that takes by weighing above-mentioned preparation
2Whisker joins in the solution that contains lead ion 20～200 mg/L, 5～40 ℃ of temperature of reaction, reaction times 150 min, wherein TiO
2The ratio of whisker and lead ion is 0.015～1.5 mg/ mg.
Above-mentioned TiO
2The method of whisker absorption chromium metal ion is carried out according to following step: the TiO that takes by weighing above-mentioned preparation
2Whisker in the solution that contains chromium 10～50 mg/L, 5～40 ℃ of temperature of reaction, reaction times 150 min, wherein TiO
2The ratio of whisker and chromium ion is 0.015～0.75 mg/ mg.
The present invention is a raw material with cheap metatitanic acid, and KOH prepares TiO for the hydro-thermal medium
2Whisker and to copper-lead chromium heavy metal absorption, the present invention has the control of being easy to, and cost is low, the advantage of technology and simple flow.Made sorbent material specific surface area reaches 300 m greatly
2/ g has big surface energy, and loading capacity is big, big many of the loading capacity of the sorbent material of having reported than zeolite powder, wilkinite etc., and also this sorbent material can not cause secondary pollution, and nontoxic, industrial prospect is arranged very much.
Description of drawings:
Fig. 1: 2 g TiO
2Normal metatitanic acid, 0.02 g trisodium citrate, regulating pH is the product sem photograph that 2,150 ℃ of reaction 18 h cooling backs add 80 mL KOH solution (4 mol/L), 100 ℃ of isothermal reaction 24 h.
Fig. 2: 8 g TiO
2Normal metatitanic acid, 0.4 g trisodium citrate, regulating pH is the product sem photograph that 2,150 ℃ of reaction 18 h cooling backs add 80 mL KOH solution (12 mol/L), 150 ℃ of isothermal reaction 96 h.
Fig. 3: 4 g TiO
2Normal metatitanic acid, 0.2 g trisodium citrate, regulating pH is the product sem photograph that 2,150 ℃ of reaction 18 h cooling backs add 80 mL KOH solution (6 mol/L), 140 ℃ of isothermal reaction 48 h.
Fig. 4: 6 g TiO
2Normal metatitanic acid, 0.20 g trisodium citrate, regulating pH is the product sem photograph that 2,150 ℃ of reaction 18 h cooling backs add 80 mL KOH solution (8 mol/L), 140 ℃ of isothermal reaction 48 h.
Embodiment
The present invention will be further described below in conjunction with concrete embodiment
Embodiment 1
With metatitanic acid (main component TiO
22g, the TiO in the metatitanic acid
2Content is 36.03%) and account for TiO
2Mass ratio is the trisodium citrate of 1%～5% content, add distilled water, regulating pH is 2, ultra-sonic dispersion 6 h, stir 4 h, reach thorough mixing, the slurry that makes is moved in the teflon-lined autoclave, under 150 ℃, react 18 h, reactor is naturally cooled to room temperature, and regulating pH is 7, adds 4 mol/L KOH solution (the contained TiO of metatitanic acid wherein
2(g/mL) is 1～4:40), and ultra-sonic dispersion 6 h stir 4 h with the quality of KOH solution and volume ratio, reach thorough mixing, the slurry that makes is moved in the teflon-lined autoclave, under 100 ℃, reaction 24h naturally cools to room temperature with reactor; Reactant is filtered, uses deionized water wash, until the specific conductivity of filtrate less than 20 mS/m; Filter cake is placed the thermostatic drying chamber inner drying, and drying temperature is 100 ℃, and be 12 h time of drying, obtains sample such as Fig. 1.
Embodiment 2
With metatitanic acid (main component TiO
28g, the TiO in the metatitanic acid
2Content is 36.03%) and account for TiO
2Mass ratio is the trisodium citrate of 1%～5% content, add distilled water, regulating pH is 2, ultra-sonic dispersion 6 h, stir 4 h, reach thorough mixing, the slurry that makes is moved in the teflon-lined autoclave, under 150 ℃, react 18 h, reactor is naturally cooled to room temperature, and regulating pH is 7, adds 12 mol/L KOH solution (the contained TiO of metatitanic acid wherein
2(g/mL) is 1～4:40), and ultra-sonic dispersion 6 h stir 4 h with the quality of KOH solution and volume ratio, reach thorough mixing, the slurry that makes is moved in the teflon-lined autoclave, under 100 ℃, reaction 24h naturally cools to room temperature with reactor; Reactant is filtered, uses deionized water wash, until the specific conductivity of filtrate less than 20 mS/m; Filter cake is placed the thermostatic drying chamber inner drying, and drying temperature is 100 ℃, and be 12 h time of drying, obtains sample such as Fig. 2.
Embodiment 3
With metatitanic acid (main component TiO
24g, the TiO in the metatitanic acid
2Content is 36.03%) and account for TiO
2Mass ratio is the trisodium citrate of 1%～5% content, add distilled water, regulating pH is 2, ultra-sonic dispersion 6 h, stir 4 h, reach thorough mixing, the slurry that makes is moved in the teflon-lined autoclave, under 150 ℃, react 18 h, reactor is naturally cooled to room temperature, and regulating pH is 7, adds 6 mol/L KOH solution (the contained TiO of metatitanic acid wherein
2(g/mL) is 1～4:40), and ultra-sonic dispersion 6 h stir 4 h with the quality of KOH solution and volume ratio, reach thorough mixing, the slurry that makes is moved in the teflon-lined autoclave, under 100 ℃, reaction 24h naturally cools to room temperature with reactor; Reactant is filtered, uses deionized water wash, until the specific conductivity of filtrate less than 20 mS/m; Filter cake is placed the thermostatic drying chamber inner drying, and drying temperature is 100 ℃, and be 12 h time of drying, obtains sample such as Fig. 3.
Embodiment 4
With metatitanic acid (main component TiO
26g, the TiO in the metatitanic acid
2Content is 36.03%) and account for TiO
2Mass ratio is the trisodium citrate of 1%～5% content, add distilled water, regulating pH is 2, ultra-sonic dispersion 6 h, stir 4 h, reach thorough mixing, the slurry that makes is moved in the teflon-lined autoclave, under 150 ℃, react 18 h, reactor is naturally cooled to room temperature, and regulating pH is 7, adds 8 mol/L KOH solution (the contained TiO of metatitanic acid wherein
2(g/mL) is 1～4:40), and ultra-sonic dispersion 6 h stir 4 h with the quality of KOH solution and volume ratio, reach thorough mixing, the slurry that makes is moved in the teflon-lined autoclave, under 100 ℃, reaction 24h naturally cools to room temperature with reactor; Reactant is filtered, uses deionized water wash, until the specific conductivity of filtrate less than 20 mS/m; Filter cake is placed the thermostatic drying chamber inner drying, and drying temperature is 100 ℃, and be 12 h time of drying, obtains sample such as Fig. 4.
Embodiment 5
Take by weighing the TiO for preparing
2 Whisker 100 mg join 300 mL by CuSO
4.6H
2In the solution of copper ions 20 mg/L of O preparation, 40 ℃ of temperature of reaction, reaction times 150 min.Belong to ionic concentration (instrument model: TAS-986) by atomic absorption spectrometry absorption back GOLD FROM PLATING SOLUTION.And calculate adsorptive capacity and be about 60 mg/g.
Embodiment 6
Take by weighing the TiO for preparing
2Whisker 80 mg join 300 mL by CuSO
46H
2In the solution of copper ions 200 mg/L of O preparation, 25 ℃ of temperature of reaction, reaction times 150 min.Belong to ionic concentration (instrument model: TAS-986) by atomic absorption spectrometry absorption back GOLD FROM PLATING SOLUTION.And calculate adsorptive capacity and be about 200 mg/g.
Embodiment 7
Take by weighing the TiO for preparing
2Whisker 50 mg join 300 mL by Pb (NO
3)
2In the solution that contains lead ion 20 mg/L of preparation, 5 ℃ of temperature of reaction, reaction times 150 min.Belong to ionic concentration (instrument model: TAS-986) by atomic absorption spectrometry absorption back GOLD FROM PLATING SOLUTION.And calculate adsorptive capacity and be about 150 mg/g.
Embodiment 8
Take by weighing the TiO for preparing
2 Whisker 100 mg join 300 mL by Pb (NO
3)
2In the solution that contains lead ion 200 mg/L of preparation, 40 ℃ of temperature of reaction, reaction times 150 min.Belong to ionic concentration (instrument model: TAS-986) by atomic absorption spectrometry absorption back GOLD FROM PLATING SOLUTION.And calculate adsorptive capacity and be about 300 mg/g.
Embodiment 9
Take by weighing the TiO for preparing
2Whisker 10 mg join 300 mL by K
2Cr
2O
7In the solution that contains chromium 10 mg/L of preparation, 5 ℃ of temperature of reaction, reaction times 150 min.Belong to ionic concentration (instrument model: TAS-986) by atomic absorption spectrometry absorption back GOLD FROM PLATING SOLUTION.And calculate adsorptive capacity and be about 10 mg/g.
Embodiment 10
Take by weighing the TiO for preparing
2 Whisker 100 mg join 300 mL by K
2Cr
2O
7In the solution that contains chromium 50 mg/L of preparation, 40 ℃ of temperature of reaction, reaction times 150 min.Belong to ionic concentration (instrument model: TAS-986) by atomic absorption spectrometry absorption back GOLD FROM PLATING SOLUTION.And calculate adsorptive capacity and be about 60 mg/g.
Claims (6)
1. TiO
2The Preparation of Whiskers method is characterized in that carrying out according to following step: (1) adds distilled water with metatitanic acid and trisodium citrate, and regulating pH is 2, and ultra-sonic dispersion 6 h stir 4 h, reach thorough mixing;
(2) slurry that makes is moved in the autoclave, under 150 ℃, react 18 h reactor is naturally cooled to room temperature, regulating pH is 7, adds 4～12 mol/L KOH solution, and ultra-sonic dispersion 6 h stir 4 h, reach thorough mixing;
(3) slurry that makes is moved in the autoclave, under 100 ℃～150 ℃, reaction 24～96h naturally cools to room temperature with reactor; Reactant is filtered, uses deionized water wash, until the specific conductivity of filtrate less than 20 mS/m; Filtration cakes torrefaction is promptly got product, and drying temperature is 100 ℃, and be 12 h time of drying.
2. a kind of TiO according to claim 1
2The Preparation of Whiskers method is characterized in that the main component in the metatitanic acid described in the step (1) wherein is TiO
2, the TiO in the metatitanic acid
2Content is 36.03%; The add-on of trisodium citrate is TiO by quality ratio
21%～5%.
3. a kind of TiO according to claim 1
2The Preparation of Whiskers method is characterized in that the wherein middle contained TiO of metatitanic acid of step (2)
2With the quality and the volume ratio of KOH solution be 1～4:40 g/mL.
4.TiO
2The method of whisker absorbing copper metal ion is characterized in that carrying out according to following step: the TiO that takes by weighing above-mentioned preparation
2Whisker joins in the solution of copper ions 20～200 mg/L, 5～40 ℃ of temperature of reaction, reaction times 150 min, wherein TiO
2The ratio of whisker and cupric ion is 0.015～1.5 mg/ mg.
5.TiO
2Whisker absorption lead metal ionic method is characterized in that carrying out according to following step: the TiO that takes by weighing above-mentioned preparation
2Whisker joins in the solution that contains lead ion 20～200 mg/L, 5～40 ℃ of temperature of reaction, reaction times 150 min, wherein TiO
2The ratio of whisker and lead ion is 0.015～1.5 mg/ mg.
6.TiO
2The method of whisker absorption chromium metal ion is characterized in that carrying out according to following step: the TiO that takes by weighing above-mentioned preparation
2Whisker in the solution that contains chromium 10～50 mg/L, 5～40 ℃ of temperature of reaction, reaction times 150 min, wherein TiO
2The ratio of whisker and chromium ion is 0.015～0.75 mg/ mg.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614872A (en) * | 2012-02-27 | 2012-08-01 | 苏州大学 | Preparation method of gold cluster/TiO2 composite nano material |
| CN102796404A (en) * | 2012-05-10 | 2012-11-28 | 江苏大学 | Method for preparing coloring composite materials by coating inorganic nano films on mica titanium |
| CN102962028A (en) * | 2012-12-14 | 2013-03-13 | 山东轻工业学院 | Preparation method of heavy metal ion adsorbent |
| CN110180557A (en) * | 2019-06-12 | 2019-08-30 | 巢湖学院 | A kind of Ag2S/TiO2The preparation method and applications of composite photo-catalyst |
| CN110725005A (en) * | 2018-07-17 | 2020-01-24 | 中国石油天然气股份有限公司 | Mesoporous TiO 22Preparation method of whisker, distillate oil hydrodesulfurization catalyst and preparation method thereof |
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|---|---|---|---|---|
| CN1699182A (en) * | 2005-06-09 | 2005-11-23 | 江苏大学 | Process for preparing rutile-type nano TiO2 by meta titanic acid |
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2011
- 2011-03-18 CN CN2011100663928A patent/CN102154697B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1699182A (en) * | 2005-06-09 | 2005-11-23 | 江苏大学 | Process for preparing rutile-type nano TiO2 by meta titanic acid |
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| 《NANO LETTERS》 20081028 Xinjian Feng等 Vertically Aligned Single Crystal TiO2 Nanowire Arrays Grown Directly on Transparent Conducting Oxide Coated Glass: Synthesis Details and Applications 3781-3786 第8卷, 第11期 * |
| 《中国有色金属学报》 20060630 蒋银花等 粒径可控金红石型纳米二氧化钛的制备及表征 1058-1063 第16卷, 第6期 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614872A (en) * | 2012-02-27 | 2012-08-01 | 苏州大学 | Preparation method of gold cluster/TiO2 composite nano material |
| CN102796404A (en) * | 2012-05-10 | 2012-11-28 | 江苏大学 | Method for preparing coloring composite materials by coating inorganic nano films on mica titanium |
| CN102962028A (en) * | 2012-12-14 | 2013-03-13 | 山东轻工业学院 | Preparation method of heavy metal ion adsorbent |
| CN102962028B (en) * | 2012-12-14 | 2014-09-03 | 山东轻工业学院 | Preparation method of heavy metal ion adsorbent |
| CN110725005A (en) * | 2018-07-17 | 2020-01-24 | 中国石油天然气股份有限公司 | Mesoporous TiO 22Preparation method of whisker, distillate oil hydrodesulfurization catalyst and preparation method thereof |
| CN110725005B (en) * | 2018-07-17 | 2021-06-01 | 中国石油天然气股份有限公司 | Mesoporous TiO 22Preparation method of whisker, distillate oil hydrodesulfurization catalyst and preparation method thereof |
| CN110180557A (en) * | 2019-06-12 | 2019-08-30 | 巢湖学院 | A kind of Ag2S/TiO2The preparation method and applications of composite photo-catalyst |
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