CN103272552B - A kind of titanate nano material and application process thereof of disposing of sewage of can be recycled - Google Patents
A kind of titanate nano material and application process thereof of disposing of sewage of can be recycled Download PDFInfo
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- CN103272552B CN103272552B CN201310167322.0A CN201310167322A CN103272552B CN 103272552 B CN103272552 B CN 103272552B CN 201310167322 A CN201310167322 A CN 201310167322A CN 103272552 B CN103272552 B CN 103272552B
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Abstract
The present invention discloses a kind of titanate nano material and application process thereof of disposing of sewage of can be recycled.Described titanate nano material preparation method, for be scattered in concentrated alkali solution by liquid phase or solid phase titanium source, to be transferred in hydrothermal reaction kettle and to carry out hydro-thermal reaction and obtain.The application process of this material, for join in waste water by layered titanate nano material, fully stirs, and staticly settles, and is separated.Can be reused by the method putting into strippant desorb for being adsorbed with organic titanate nano material, then can be reused by the mode of ion-exchange for the layered titanate nano material containing heavy metal ion.The method effectively can remove Organic substance in water and heavy metal ion material, and reusable, has cost low, the advantages such as applicability is wide.
Description
Technical field
The present invention relates to the technical field of nano material Synthesis and applications, specific design be a kind of method of Synthesis and applications of the titanate nano material of disposing of sewage that can be recycled.
Background technology
Nano titanium oxide is a kind of important nano material, has the characteristics such as stability is high, nontoxic, biological stability is good, UV absorption, has broad application prospects at environment, information, material, the energy, medical treatment and health field.Other advantageous properties many of titanium dioxide nano material come into one's own in recent years, and have broad application prospects.Therefore, the titanium dioxide nano material of Synthesis and applications specific morphology becomes the focus of people's research.
In early days, TiO
2the preparation research of nano material mainly concentrates on nano particle, utilizes the chemical methodes such as sol-gel, can be obtained the TiO of anatase and rutile-type by calcination processing
2nano particle.In recent years, hydro-thermal method people are utilized successfully to prepare Anatase TiO again
2nanotube and TiO
2nanobelt.But, for the TiO of specific morphology
2the Synthesis and applications of nano material, the especially Synthesis and applications of laminar nano titanate also lack relevant system report.Existing research is still mainly devoted to synthesize TiO
2doping vario-property Application of micron is studied in photocatalysis, does not also prepare laminar nano titanate so far for removing the research report of Organic substance in water and heavy metal ion.
Summary of the invention
For defect of the prior art, the object of this invention is to provide and a kind of prepare laminar nano titanate by adjusting hydrothermal reaction response thing addition and reaction condition, for removing heavy metal ion and organic matter in water and recycled method.
According to an aspect of the present invention, a kind of preparation method of the titanate nano material of disposing of sewage that can be recycled is provided, the steps include:
(1) solid phase or liquid phase titanium source are scattered in concentrated alkali solution, fully stir, obtain suspension; The concentration of described concentrated alkali solution is 9 ~ 11 mol/L, and the mass ratio of titanium source and concentrated base is 1:8 ~ 1:14;
(2) transfer in hydrothermal reaction kettle by gained suspension, under 120 ~ 180 degree, carry out hydro-thermal reaction, products therefrom washing, drying, obtain layered titanate nano material.
Preferably, the solid phase titanium source described in step (1) comprises in rutile titanium dioxide, anatase titanium dioxide, P25 type titanium dioxide etc. a kind of; Liquid phase titanium source comprises in butyl titanate, isopropyl titanate etc. a kind of; Concentrated base comprises in NaOH, potassium hydroxide etc. a kind of.
Preferably, described method adopts solid phase titanium source TiO
2nano powder and concentrated NaOH solution react, and are specially: the TiO taking mass ratio as 1:10 ~ 1:14
2nano powder and NaOH are raw material; By TiO
2nano-powder dispersion is in the NaOH aqueous solution of 9 ~ 11 mol/L, stir 20 ~ 30 minutes, in the hydrothermal reaction kettle that the suspension obtained is transferred to, hydro-thermal reaction is carried out 12 ~ 36 hours under 120-180 degree, obtain white product, deionized water washing, to close to neutral, dried, is obtained laminar nano titanate.
Preferably, described method adopts liquid phase titanium source and dense KOH solution to react, and is specially: take mass ratio as liquid phase titanium source and the KOH of 1:8 ~ 1:11 be raw material; By TiO
2nano-powder dispersion is in the KOH aqueous solution of 9 ~ 11 mol/L, stir 20 ~ 30 minutes, in the hydrothermal reaction kettle that the suspension obtained is transferred to, hydro-thermal reaction is carried out 12 ~ 36 hours under 120-180 degree, obtain white product, deionized water washing, to close to neutral, dried, is obtained laminar nano titanate.
According to an aspect of the present invention, a kind of above-mentioned obtained titanate nano material application process is provided, be specially: above-mentioned obtained layered titanate nano material is joined refuse concentration in the waste water of 10 ~ 100 mg/litre, the layered titanate nano material added and the mass ratio of waste water are 1:20 ~ 1:200, stir 1 ~ 2 hour, staticly settle, mud-water separation, clearance can reach more than 90%.
Layered titanate nano material of the present invention recycles scheme and is specifically divided into organic matter desorb and heavy metal ion to exchange two technical schemes, and each technical scheme is as follows.
Organic matter desorb scheme is: will be adsorbed with organic layered titanate nano material and leach, and be washed with distilled water to close to neutral, add strippant, ambient temperatare is put and carried out desorb, and period constantly stirs.Layered titanate nano material after desorb still has the ability removing Organic substance in water and heavy metal ion.Described strippant is made up of the three kinds or more in following material: highly basic (pure highly basic, does not have water), methyl alcohol, ethanol, acetone, and mixing time is 30 minutes ~ 2 hours.
Heavy metal ion exchange scheme is: the sediment obtained after separation is put into dust technology, adjust ph to 3 ~ 6, stirs.By products therefrom suction filtration, spend deionized water.Products therefrom is put into NaOH (or potassium hydroxide) solution of 1 mol/L, stir, suction filtration, spends deionized water again, and products therefrom is dried, and obtains layered titanate nano material.This product still has the ability removing Organic substance in water and heavy metal ion equally.Described NaOH or potassium hydroxide solution concentration are 0.5 ~ 2 mol/L, and mixing time is 12 ~ 36 hours.
Compared with prior art, the present invention has following beneficial effect:
Laminar nano titanate of the present invention can recycle removes heavy metal ion and organic matter in water.Instant invention overcomes the deficiencies in the prior art, for the waste water of concentration in 10 ~ 100 mg/litre, through the stirring of 1 ~ 2 hour, clearance has exceeded 90%, and can reuse, there is significant economic benefit and social benefit, have broad application prospects in field of waste water treatment.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the X-ray diffractogram spectrogram of the laminar nano titanate that embodiment 1 obtains.
Fig. 2 is the stereoscan photograph of the laminar nano titanate that embodiment 1 obtains.
Fig. 3 is the X-ray diffractogram spectrogram of the laminar nano titanate that embodiment 2 obtains.
Fig. 4 is the stereoscan photograph of the laminar nano titanate that embodiment 2 obtains.
Fig. 5 is embodiment 1, and poisonous and harmful substance experimental result picture in water removed by the 2 laminar nano titanates obtained.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
Embodiment 1
By 2.5 grams of commercial P25 type titanium dioxide powder (goldschmidt chemical corporation P25 type titanium dioxide, rutile is 3:7 with the ratio of anatase, average grain diameter 30 nanometer) to be scattered in 75 ml concns be in the sodium hydroxide solution of 9 mol/L, be placed in beaker fully to stir 20 minutes, gained suspension is transferred in the hydrothermal reaction kettle (volume 100 milliliters) of polytetrafluoroethylliner liner, hydro-thermal reaction 36 hours under 120 degree.By precipitated product deionized water and watery hydrochloric acid washing after reaction terminates, until cleaning solution is close to neutral, after dry process, obtain layered titanate nano material.
Obtained product characterizes its structure and crystal formation with XRD, SEM respectively, and Fig. 1,2 is respectively XRD and the SEM collection of illustrative plates of the laminar nano titanate powder of preparation.Characterization result display products therefrom is Detitanium-ore-type TiO
2with sodium titanate (Na
2ti
3o
7) mixed crystal type nanometer line, degree of crystallinity is good, and nanowire width is 20 ~ 80 nanometers, and length is 200 ~ 400 nanometers.
Fig. 5 is embodiment 1, and poisonous and harmful substance experimental result picture in water removed by the 2 laminar nano titanates obtained.
Use obtained layered titanate nano material to purify the waste water from dyestuff that 1000 milliliters contain rhodamine B, the concentration of rhodamine B is 10 mg/litre, and the dosage of layered titanate is 1.0 grams.Rhodamine B concentration in embodiment 1 with mixing time change as shown in Figure 5, to stir after one hour the clearance of rhodamine B more than 95.0%.
Leached by the layered titanate being adsorbed with rhodamine B, be washed with distilled water to close to neutral, add the strippant 20 milliliters be mixed into by NaOH, methyl alcohol, acetone, stirred at ambient temperature carries out the desorb of rhodamine b for 1 hour, and period constantly stirs.
Measured by ultraviolet light absorption, strippant reaches 80% for the desorption efficiency of rhodamine B.
Embodiment 2
It is in the KOH solution of 11 mol/L that 5 milliliters of butyl titanates (TBOT) are scattered in 75 ml concns, be placed in beaker fully to stir 30 minutes, gained suspension is transferred in the hydrothermal reaction kettle (volume 100 milliliters) of polytetrafluoroethylliner liner, hydro-thermal reaction 12 hours under 140 degree.By precipitated product deionized water and watery hydrochloric acid washing after reaction terminates, until cleaning solution is close to neutral, after dry process, obtain layered titanate nano material.
Obtained product characterizes its structure and crystal formation with XRD, SEM respectively, and Fig. 3,4 is respectively XRD and the SEM collection of illustrative plates of the laminar nano titanate powder of preparation.Result display products therefrom is anatase type tio2 and potassium titanate (K
2ti
3o
7) mixed crystal type nanometer band, degree of crystallinity is good, and nanobelt width is 20 ~ 60 nanometers, and length is 200 ~ 300 nanometers.
Fig. 5 is embodiment 1, and poisonous and harmful substance experimental result picture in water removed by the 2 laminar nano titanates obtained.
Use obtained layered titanate nano material to purify the wastewater from chemical industry that 1000 milliliters contain ferric trichloride, the concentration of ferric trichloride is 100 mg/litre, and the dosage of layered titanate is 1.0 grams.Three greening concentration of iron in embodiment 2 with mixing time change as shown in Figure 5, to stir after 1 hour the clearance of ferric trichloride more than 95.0%.
Layered titanate containing iron ion is leached, puts into dust technology, adjust ph to 4, stir 24 hours.By products therefrom suction filtration, spend deionized water, put into the KOH solution of 0.5 mol/L after drying, stir 12 hours, suction filtration, deionized water is washed, and dries, and reclaims and obtains laminar nano titanate, still can heavy-metal ion removal and organic matter.
Embodiment 3
By 2.5 grams of commercial P25 type titanium dioxide powder (goldschmidt chemical corporation P25 type titanium dioxide, rutile is 3:7 with the ratio of anatase, average grain diameter 30 nanometer) to be scattered in 75 ml concns be in the sodium hydroxide solution of 10 mol/L, be placed in beaker fully to stir 25 minutes, gained suspension is transferred in the hydrothermal reaction kettle (volume 100 milliliters) of polytetrafluoroethylliner liner, hydro-thermal reaction 24 hours under 180 degree.By precipitated product deionized water and watery hydrochloric acid washing after reaction terminates, until cleaning solution is close to neutral, after dry process, obtain layered titanate nano material.
Use obtained layered titanate nano material to purify the waste water from dyestuff that 1000 milliliters contain rhodamine B, the concentration of rhodamine B is 100 mg/litre, and the dosage of layered titanate is 1.0 grams.To stir after 1 hour the clearance of rhodamine B more than 95.0%.
Leached by the layered titanate being adsorbed with rhodamine B, be washed with distilled water to close to neutral, add the strippant 20 milliliters be mixed into by potassium hydroxide, methyl alcohol, acetone, ethanol, ambient temperatare puts the desorb that 3 hours carry out rhodamine B, and period constantly stirs.
Measured by ultraviolet light absorption, strippant reaches 80% for the desorption efficiency of rhodamine B.
Embodiment 4
It is in the KOH solution of 11 mol/L that 5 milliliters of butyl titanates (TBOT) are scattered in 75 ml concns, be placed in beaker fully to stir 30 minutes, gained suspension is transferred in the hydrothermal reaction kettle (volume 100 milliliters) of polytetrafluoroethylliner liner, hydro-thermal reaction 36 hours under 180 degree.By precipitated product deionized water and watery hydrochloric acid washing after reaction terminates, until cleaning solution is close to neutral, after dry process, obtain layered titanate nano material.
Use obtained layered titanate nano material to purify the wastewater from chemical industry that 1000 milliliters contain ferric trichloride, the concentration of ferric trichloride is 50 mg/litre, and the dosage of layered titanate is 1.0 grams.To stir after 1 hour the clearance of ferric trichloride more than 99.0%.
Laminar nano titanate containing iron ion is leached, puts into dust technology, adjust ph to 4, stir 24 hours.By products therefrom suction filtration, spend deionized water, put into the NaOH solution of 1 mol/L after drying, stir 36 hours, suction filtration, deionized water is washed, and dries, and reclaims and obtains laminar nano titanate, still can heavy-metal ion removal and organic matter.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (6)
1. the application process of the titanate nano material of disposing of sewage that can be recycled, it is characterized in that described titanate nano material is for removing heavy metal ion and organic matter in water, that is: described titanate nano material is joined the refuse concentration of wish purification in the waste water of 10 ~ 100 mg/litre, the layered titanate nano material added and the mass ratio of waste water are 1:20 ~ 1:200, stir, staticly settle, mud-water separation, namely clearance reaches more than 90%;
Preparation method's step of described titanate nano material is:
(1) solid phase or liquid phase titanium source are scattered in concentrated alkali solution, fully stir, obtain suspension; The concentration of described concentrated alkali solution is 9 ~ 11 mol/L, and the mass ratio of titanium source and concentrated base is 1:8 ~ 1:14;
(2) transfer in hydrothermal reaction kettle by gained suspension, under 120 ~ 180 degree, carry out hydro-thermal reaction, products therefrom washing, drying, obtain layered titanate nano material;
Described solid phase titanium source is a kind of in rutile titanium dioxide, anatase titanium dioxide, P25 type titanium dioxide; Described liquid phase titanium source is a kind of in butyl titanate, isopropyl titanate; Described concentrated base is a kind of in NaOH, KOH;
Described method adopts solid phase titanium source TiO
2nano powder and concentrated NaOH solution react, and are specially: the TiO taking mass ratio as 1:10 ~ 1:14
2nano powder and NaOH are raw material; By TiO
2nano-powder dispersion, in the NaOH aqueous solution of 9 ~ 11 mol/L, stirs 20 ~ 30 minutes, in the hydrothermal reaction kettle that the suspension obtained is transferred to, under 120-180 degree, carry out hydro-thermal reaction, obtain white product, deionized water washing is to close neutral, dry, obtain laminar nano titanate;
Described method adopts liquid phase titanium source and dense KOH solution to react, and is specially: take mass ratio as liquid phase titanium source and the KOH of 1:8 ~ 1:11 be raw material; Liquid phase titanium source is scattered in the KOH aqueous solution of 9 ~ 11 mol/L, stirs 20 ~ 30 minutes, in the hydrothermal reaction kettle that the suspension obtained is transferred to, under 120-180 degree, carry out hydro-thermal reaction, obtain white product, deionized water washing is to close neutral, dry, obtain laminar nano titanate.
2. the application process of the titanate nano material of disposing of sewage that can be recycled according to claim 1, is characterized in that: the described hydro-thermal reaction time is 12 ~ 36 hours.
3. the application process of the titanate nano material of disposing of sewage that can be recycled according to claim 1, it is characterized in that: the described titanate nanometer ratio added in described waste water to be clean is 0.8 ~ 1.3 grams per liter, mixing time is 30 minutes ~ 2 hours.
4. the application process of the titanate nano material of disposing of sewage that can be recycled according to claim 1, is characterized in that: layered titanate nano material can recycle when exchanging for organic matter desorb or heavy metal ion, is specially:
For organic matter desorb: organic layered titanate nano material will be adsorbed with and leach, be washed with distilled water to close to neutral, add strippant, ambient temperatare is put and is carried out desorb, period constantly stirs, and the layered titanate nano material after desorb still has the ability removing Organic substance in water and heavy metal ion; Described strippant is made up of the three kinds or more in following material: highly basic, methyl alcohol, ethanol, acetone;
Heavy metal ion exchanges: the sediment obtained after separation is put into diluted acid, adjust ph to 3 ~ 6, stirs, by products therefrom suction filtration, spends deionized water; Again products therefrom is put into NaOH or KOH solution, stir, suction filtration, spends deionized water, and products therefrom is dried, and obtains layered titanate nano material, and this product still has the ability removing Organic substance in water and heavy metal ion equally.
5. the application process of the titanate nano material of disposing of sewage that can be recycled according to claim 4, is characterized in that: described diluted acid is a kind of in dust technology, watery hydrochloric acid.
6. the application process of the titanate nano material of disposing of sewage that can be recycled according to claim 4, it is characterized in that: described NaOH or KOH solution concentration are 0.5 ~ 2 mol/L, mixing time is 12 ~ 36 hours.
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| CN103641262B (en) * | 2013-12-23 | 2015-04-22 | 环境保护部华南环境科学研究所 | Method for recycling heavy metals in electroplating wastewater by using modified titanium nanotube |
| CN104857915B (en) * | 2015-03-26 | 2018-05-01 | 沈阳理工大学 | A kind of method that porous titanate adsorbent is prepared using sludge |
| CN104857916A (en) * | 2015-03-26 | 2015-08-26 | 沈阳理工大学 | Method for preparing porous calcium titanate by using ammoniation sludge |
| CN105964309A (en) * | 2016-05-12 | 2016-09-28 | 中国科学院合肥物质科学研究院 | Titanate core shell micro-nano structure ion exchange material and preparation method thereof |
| CN106563409A (en) * | 2016-10-11 | 2017-04-19 | 海南大学 | Modified titanic acid nano-material and preparation method thereof |
| CN113336335B (en) * | 2021-06-01 | 2022-01-14 | 湖北亮绿环保技术有限公司 | Nano material for industrial and chemical sewage treatment and preparation method thereof |
| CN114291843B (en) * | 2022-01-07 | 2023-09-29 | 中国科学院东北地理与农业生态研究所 | Multistage sodium titanate microtube and preparation method and application thereof |
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