CN101279789A - Method for processing polluted water with iron-titanium composite oxide nano-material - Google Patents
Method for processing polluted water with iron-titanium composite oxide nano-material Download PDFInfo
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- CN101279789A CN101279789A CNA2008100434132A CN200810043413A CN101279789A CN 101279789 A CN101279789 A CN 101279789A CN A2008100434132 A CNA2008100434132 A CN A2008100434132A CN 200810043413 A CN200810043413 A CN 200810043413A CN 101279789 A CN101279789 A CN 101279789A
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Abstract
The invention provides a method adopting an iron-titanium composite oxide nano-material to treat the polluted water, which comprises the following steps of: making the iron-titanium composite oxide nano-material contact with a water body containing organic pollutants and heavy metal ions for three to twelve hours in the open environment, removing the organic pollutants and the heavy metal ions in the water body through the catalytic oxidation and adsorption functions, and reaching the purification of the water body; and the nano-material is synthesized by a ferric salt with a valence of 3 and a titanium salt with a valence of 4, wherein the mole fraction of the iron with a valence of 3 is between 20 percent and 80 percent. Compared with the prior art, the invention applies the iron-titanium composite oxide nano-material to the polluted water body for treatment, particularly to the ground water and drinking water for removing arsenic-humic acid and chromium-humic acid combined pollutants. The method has advantages of low material consumption, low cost, simple operation, fast treatment speed, non secondary pollution and small extent of influence by environmental factors.
Description
Technical field
The present invention relates to a kind of method of handling polluted water.
Background technology
In recent years, nano material is widely used in all trades and professions owing to having significant advantageous characteristic.
Wherein, nano titanium oxide is widely used in the environmental chemical engineering field as a kind of typical photocatalyst.Many bibliographical informations the effective agricultural chemicals in the catalyzed degradation environment of titanium dioxide nanoparticle, organism such as polychlorobiphenyl, polycyclic aromatic hydrocarbons and humic acid.Yet, in the polluted water body of reality, and since the diversity of source of pollution, normally multiple pollutent coexistence in the water body, and wherein the organic combined pollutant of heavy metal is the most representative.For this pollutant, although nano titanium oxide is photocatalysis degradation organic contaminant effectively, yet the environmental risk of bringing thus is that the heavy metal with the organic pollutant complexing might be released in the water body again, thereby must adopt the step-by-step processing method further remove heavy metal.
The nano-sized iron oxide particle is a kind of effective sorbing material.Studies confirm that in a large number ferric oxide can the active adsorption heavy metal ion, as arsenic, chromium etc.In addition, correlative study confirms that also iron mixing in titanium oxide can make the effective wavelength generation red shift of titanium dioxide generation photocatalysis.Correlative study also confirms, in a kind of preparation process of metal oxide, mixes another kind of metal ion, can obtain more tiny uniform and stable nano particle, thereby can increase particulate specific surface area and loading capacity.Therefore, how utilizing iron-titanium composite oxide nano-material to handle polluted water, is a crucial problem.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of material usage few for the defective that overcomes above-mentioned prior art existence, and cost is low, and is simple to operate, and processing speed is fast, and the employing iron-titanium composite oxide nano-material of non-secondary pollution is handled the method for polluted water.
Method of the present invention comprises the steps:
Iron-titanium composite oxide nano-material is contacted 3～12 hours with the water body that contains organic pollutant and heavy metal ion under open environment, organic pollutant and heavy metal ion by in catalyzed oxidation and the adsorption removal water body reach water body purification;
The consumption of described iron-titanium composite oxide nano-material in water treatment is 0.2～2g/L, and the appropriate pH scope is 4～10, and temperature range is 2～60 ℃;
In the described iron-titanium composite oxide nano-material+molar fraction of 4 valency titaniums is 20%～80%;
Organic pollutant in the described water body and heavy metal ion comprise arsenic-humic acid combined pollutant or chromium-humic acid combined pollutant;
In the water body:
In arsenic-humic acid combined pollutant, humic acid concentration is 0.1～10mg/L, and the concentration of arsenic is 0.05～5mg/L;
In chromium-humic acid combined pollutant, humic acid concentration is 0.1～10mg/L, and chromium concn is 0.05～10mg/L;
Described open environment comprises that water body directly is exposed under the sunlight or at indoor ultra violet lamp, effectively carries out to impel catalytic oxidation process;
The median size of described iron-titanium composite oxide nano-material is the porous material of 5～200 μ m, and mean pore size is 2～20nm;
This nano material is synthetic by+3 valency molysite and+4 valency titanium salts, and wherein+3 the molar fraction of valency iron is 20%～80%;
Described+3 valency molysite comprise iron(ic) chloride, iron nitrate or ferric sulfate;
Described+4 valency titanium salts comprise titanium chloride, Titanium Nitrate or titanium sulfate;
The preparation method of above-mentioned iron-titanium composite oxide nano-material may further comprise the steps:
(1)+4 valency titanium salts and+3 valency molysite are mixed, add water and generate the ferrotitanium mixing solutions, wherein+4 the concentration of valency titanium salt is 0.01～0.5mol/L, the concentration 0.01～0.5mol/L of+3 valency molysite;
(2) regulate above-mentioned mixing solutions pH to 7～11 with basic solution, generate throw out;
(3) throw out that generates is washed with water after, the diameter that the semipermeable membrane material of packing into is made is in the long tube bag of 5cm;
(4) with the semi-permeable membranes sealing, use water rinse, change deionized water, lead being stabilized in 0.8～1.0 μ S/cm until the electricity of water;
(5) with the throw out in the above-mentioned semi-permeable membranes subzero 60 ℃ of lyophilizes at least 24 hours or 60～105 ℃ of dryings after at least 24 hours, 300～700 ℃ of roastings, obtain light yellow, red-brown or brown granular, be product;
Said semi-permeable membranes is a kind of and gives the film that inorganic ion sees through in the solution, can adopt the commercially available prod, as the D5 semi-permeable membranes of Japanese Wako Pure Chemical Industries, Ltd..
Described+3 valency molysite are one or more mixtures in iron(ic) chloride, iron nitrate or the ferric sulfate;
Described+4 valency titanium salts are one or more mixtures in titanium chloride, Titanium Nitrate or the titanium sulfate;
Described basic solution is 0.1～1.0mol/L sodium hydroxide or potassium hydroxide solution.
Compared with prior art, the present invention is applied to polluted water body with a kind of iron-titanium composite oxide nano-material and handles, and particularly is applied to remove in underground water and the tap water arsenic-humic acid, chromium-humic acid combined pollutant.This method has that material usage is few, and cost is low, and is simple to operate, and processing speed is fast, and non-secondary pollution is subjected to advantages such as the environmental factor influence degree is little.
Embodiment
Embodiment 1
The preparation of iron-titanium composite oxide nano-material:
Adopt iron(ic) chloride conduct+3 valency molysite, titanium chloride conduct+4 valency titanium salts adds distilled water constant temperature and stirs and generate the ferrotitanium mixing solutions, and iron and the titanium volumetric molar concentration in mixing solutions is respectively 0.04 and 0.16mol/L.
Sodium hydroxide solution with 0.5mol/L dropwise joins in the above mixing solutions, and constant temperature stirs, and is 7.0 until pH value of solution.
Stop to add sodium hydroxide solution, continue constant temperature and stir after two hours, cover and left standstill 12 hours, topple over upper strata liquid, use twice of deionized water rinsing throw out.
Throw out is packed in the bag of being made by semi-permeable membranes, semi-permeable membranes is placed the container balance that deionized water is housed, changed deionized water once in per 24 hours, the electricity of deionized water is led continuous three days less than 1.0 μ S/cm in container.
Throw out is transferred in the beaker of freeze drier,, obtained light yellow particle subzero 60 ℃ of lyophilizes 24 hours.The apparent median size of this particle is between 10-100 μ m, and specific surface area is 399.8m
2/ g, TEM (transmission electron microscope) analysis, above particle is formed by the particles agglomerate of particle diameter by 1-10nm, and the XRD characterization result confirms that above particle is the indefiniteness structure.
600 ℃ of roastings 8 hours, it was main obtaining by anatase octahedrite, contains the crystal grain of part rutile and ferric oxide with above light yellow particle.
Embodiment 2
Certain underground water with arsenic-humic acid combined pollution is process object, handles under following condition:
Iron-titanium composite oxide nano-material put into by the concentration of 2g/L fill in the phreatic Glass Containers, under solar radiation, stirred 5 hours, stop afterwards stirring, static 10 minutes, get supernatant liquor and carry out composition analyses such as arsenic, humic acid, the results are shown in following table:
In the described iron-titanium composite oxide nano-material+molar fraction of 4 valency titaniums is 40%;
Iron-titanium composite oxide nano-material is the porous material of median size 100 μ m, and the material mean pore size is 10nm;
Embodiment 3
Certain underground water with chromium-humic acid combined pollution is process object, handles under following condition:
Iron-titanium composite oxide nano-material put into by the concentration of 2g/L fill in the phreatic Glass Containers, under solar radiation, stirred 5 hours, stop afterwards stirring, static 10 minutes, get supernatant liquor and carry out composition analyses such as chromium, humic acid, the results are shown in following table:
In the described iron-titanium composite oxide nano-material+molar fraction of 4 valency titaniums is 60%;
Iron-titanium composite oxide nano-material is the porous material of median size 50 μ m, and the material mean pore size is 10nm;
Embodiment 4
Certain underground water with arsenic-humic acid combined pollution is process object, handles in following condition:
Iron-titanium composite oxide nano-material put into by the concentration of 1g/L fill in the phreatic Glass Containers, under indoor ultra violet lamp, stirred 3 hours, stop afterwards stirring static 10 minutes, get supernatant liquor and carry out composition analyses such as arsenic, humic acid, the results are shown in following table:
In the described iron-titanium composite oxide nano-material+molar fraction of 4 valency titaniums is 30%;
Described iron-titanium composite oxide nano-material is the porous material of median size 10 μ m, and the material mean pore size is 10nm;
Embodiment 5
Iron-titanium composite oxide nano-material is pressed the concentration of 0.2g/L, at pH is 4,2 ℃ of temperature, handle the water body of arsenic-humic acid combined pollution, humic acid concentration in the combined pollutant is 0.1mg/L, and arsenic concentration is 0.05mg/L, fully contacts 3 hours with water body under solar radiation, after catalyzed oxidation and adsorption, humic acid and arsenic in the water body are removed fully.
In the described iron-titanium composite oxide nano-material+molar fraction of 4 valency titaniums is 40%
Described iron-titanium composite oxide nano-material is the porous material of median size 100 μ m, and the material mean pore size is 20nm;
Embodiment 6
Iron-titanium composite oxide nano-material is pressed the concentration of 2g/L, at pH is 10,60 ℃ of temperature, handle the water body of arsenic-humic acid combined pollution, humic acid concentration in the combined pollutant is 10mg/L, and arsenic concentration is 5mg/L, fully contacts 12 hours with water body under ultra violet lamp, by humic acid and the arsenic in catalyzed oxidation and the adsorption removal water body, reach the purpose of water body purification.In the described iron-titanium composite oxide nano-material+and the molar fraction of 4 valency titaniums is 50%, and the iron-titanium composite oxide nano-material median size is the porous material of 55 μ m, and mean pore size is 10nm.
Embodiment 7
With the concentration that iron-titanium composite oxide nano-material is pressed 0.2g/L, be 4 at pH, 2 ℃ of temperature, the water body of processing chromium-humic acid combined pollution, humic acid concentration is 0.1mg/L in the combined pollutant, chromium concn is 0.05mg/L.Under solar radiation, fully contact 3 hours,, reach the purpose of water body purification by humic acid and the chromium in catalyzed oxidation and the adsorption removal water body with water body.In the described iron-titanium composite oxide nano-material+molar fraction of 4 valency titaniums is 60%;
Described iron-titanium composite oxide nano-material is the porous material of median size 90 μ m, and the material mean pore size is 18nm;
Embodiment 8
With the concentration that iron-titanium composite oxide nano-material is pressed 2g/L, be 10 at pH, 60 ℃ of temperature, the water body of processing chromium-humic acid combined pollution, humic acid concentration is 10mg/L in the combined pollutant, chromium concn is 10mg/L.Under ultra violet lamp, fully contact 12 hours,, reach the purpose of water body purification by humic acid and the chromium in catalyzed oxidation and the adsorption removal water body with water body.In the described iron-titanium composite oxide nano-material+and the molar fraction of 4 valency titaniums is 80%, and iron-titanium composite oxide nano-material is the porous material of median size 10 μ m, and the mean pore size of material is 2nm.
Claims (8)
1. method that adopts iron-titanium composite oxide nano-material to handle polluted water, it is characterized in that, comprise the steps: iron-titanium composite oxide nano-material is contacted 3～12 hours with the water body that contains organic pollutant and heavy metal ion under open environment, organic pollutant and heavy metal ion by in catalyzed oxidation and the adsorption removal water body reach water body purification;
Described nano material is synthetic by+3 valency molysite and+4 valency titanium salts, and wherein+3 the molar fraction of valency iron is 20%～80%.
2. method according to claim 1 is characterized in that, the median size of described iron-titanium composite oxide nano-material is the porous material of 5～200 μ m, and mean pore size is 2～20nm.
3. method according to claim 1 and 2 is characterized in that, the consumption of described iron-titanium composite oxide nano-material in water treatment is 0.2～2g/L, and the pH scope is 4～10, and temperature range is 2～60 ℃.
4. method according to claim 1 and 2 is characterized in that, organic pollutant in the described water body and heavy metal ion are arsenic-humic acid combined pollutant.
5. method according to claim 1 and 2 is characterized in that, organic pollutant in the described water body and heavy metal ion are chromium-humic acid combined pollutant.
6. method according to claim 4 is characterized in that, in the water body: in arsenic-humic acid combined pollutant, humic acid concentration is 0.1～10mg/L, and the concentration of arsenic is 0.05～5mg/L.
7. method according to claim 5 is characterized in that, in the water body: in chromium-humic acid combined pollutant, humic acid concentration is 0.1～10mg/L, and chromium concn is 0.05～10mg/L.
8. method according to claim 1 and 2 is characterized in that, described open environment is that water body directly is exposed under the sunlight or at indoor ultra violet lamp.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785988A (en) * | 2009-01-23 | 2010-07-28 | 中国科学院金属研究所 | Polynary metal oxide arsenic adsorbent material and preparation method and application thereof |
| CN102249364A (en) * | 2011-07-21 | 2011-11-23 | 南京理工大学 | Method for removing low-concentration pentavalent arsenic out of water by adsorption of iron-carrying titanium dioxide nanotubes |
| CN102745764A (en) * | 2012-07-20 | 2012-10-24 | 陕西科技大学 | Method of using aluminum-titanium composite tanning wastes to remove trivalent chromium in chrome tanning wastewater |
| CN103030189A (en) * | 2012-12-21 | 2013-04-10 | 广东工业大学 | Method for absorbing and removing trivalent arsenic in photo-catalytic oxidation drinking water |
| CN105439269A (en) * | 2015-12-16 | 2016-03-30 | 无锡吉进环保科技有限公司 | Inorganic nano flocculating agent namely metal ions loaded attapulgite |
| CN105983385A (en) * | 2015-02-05 | 2016-10-05 | 南京理工大学 | Arsenic-removal composite material and preparation method thereof |
| CN106111049A (en) * | 2016-07-12 | 2016-11-16 | 佛山杰致信息科技有限公司 | A kind of heavy metal containing sewage absorption nano composite material and preparation method thereof |
| CN107312204A (en) * | 2017-06-27 | 2017-11-03 | 福建省农业科学院农业工程技术研究所 | Based on the chitosan ferrotitanium polymeric material and its preparation for removing organic matter of sewage |
| CN108262002A (en) * | 2018-02-24 | 2018-07-10 | 北京师范大学 | A kind of preparation method and application for the Fe-Ti binary oxide adsorbents for removing antimony |
| CN112897743A (en) * | 2021-01-20 | 2021-06-04 | 中南大学 | Gradient adsorption and recovery method for heavy metals in wastewater based on magnetic titanium-containing mineral/humic acid composite adsorption material |
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2008
- 2008-05-26 CN CN2008100434132A patent/CN101279789B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785988A (en) * | 2009-01-23 | 2010-07-28 | 中国科学院金属研究所 | Polynary metal oxide arsenic adsorbent material and preparation method and application thereof |
| CN101785988B (en) * | 2009-01-23 | 2013-09-25 | 中国科学院金属研究所 | Polynary metal oxide arsenic adsorbent material and preparation method and application thereof |
| CN102249364A (en) * | 2011-07-21 | 2011-11-23 | 南京理工大学 | Method for removing low-concentration pentavalent arsenic out of water by adsorption of iron-carrying titanium dioxide nanotubes |
| CN102745764A (en) * | 2012-07-20 | 2012-10-24 | 陕西科技大学 | Method of using aluminum-titanium composite tanning wastes to remove trivalent chromium in chrome tanning wastewater |
| CN103030189A (en) * | 2012-12-21 | 2013-04-10 | 广东工业大学 | Method for absorbing and removing trivalent arsenic in photo-catalytic oxidation drinking water |
| CN105983385A (en) * | 2015-02-05 | 2016-10-05 | 南京理工大学 | Arsenic-removal composite material and preparation method thereof |
| CN105439269A (en) * | 2015-12-16 | 2016-03-30 | 无锡吉进环保科技有限公司 | Inorganic nano flocculating agent namely metal ions loaded attapulgite |
| CN106111049A (en) * | 2016-07-12 | 2016-11-16 | 佛山杰致信息科技有限公司 | A kind of heavy metal containing sewage absorption nano composite material and preparation method thereof |
| CN107312204A (en) * | 2017-06-27 | 2017-11-03 | 福建省农业科学院农业工程技术研究所 | Based on the chitosan ferrotitanium polymeric material and its preparation for removing organic matter of sewage |
| CN107312204B (en) * | 2017-06-27 | 2019-06-21 | 福建省农业科学院农业工程技术研究所 | For removing chitosan ferrotitanium polymeric material and its preparation of organic matter of sewage |
| CN108262002A (en) * | 2018-02-24 | 2018-07-10 | 北京师范大学 | A kind of preparation method and application for the Fe-Ti binary oxide adsorbents for removing antimony |
| CN108262002B (en) * | 2018-02-24 | 2021-03-02 | 北京师范大学 | Preparation method and application of Fe-Ti binary oxide adsorbent for removing antimony |
| CN112897743A (en) * | 2021-01-20 | 2021-06-04 | 中南大学 | Gradient adsorption and recovery method for heavy metals in wastewater based on magnetic titanium-containing mineral/humic acid composite adsorption material |
| CN112897743B (en) * | 2021-01-20 | 2022-05-10 | 中南大学 | Gradient adsorption and recovery method for heavy metals in wastewater based on magnetic titanium-containing mineral/humic acid composite adsorption material |
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