CN101638218B - Nano composite material, preparation method and application thereof - Google Patents
Nano composite material, preparation method and application thereof Download PDFInfo
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- CN101638218B CN101638218B CN200910090546XA CN200910090546A CN101638218B CN 101638218 B CN101638218 B CN 101638218B CN 200910090546X A CN200910090546X A CN 200910090546XA CN 200910090546 A CN200910090546 A CN 200910090546A CN 101638218 B CN101638218 B CN 101638218B
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Abstract
The invention discloses a nano composite material, a preparation method and the application thereof. The method comprises steps: evenly attaching organic solution of metallic oxide precursor on the surface and in hole channels of porous material; transforming the metallic oxide precursor into the corresponding metallic oxide by in-situ chemical reaction; and obtaining the nano composite material. The invention utilizes the hole channel structure and the large specific surface of the porous material to lead nano material of the metallic oxide to be evenly attached on the surface of the porous material. The method is simple in technique, safe, low in cost, suitable for large-scale production, low in toxicity of solvent in a reaction system, and little in environmental pollution; the prepared nano composite material can be used for absorbing and removing heavy metal ions in the water, and has remarkable effect, thus purifying the water resource which is not suitable for drinking into drinking water being in accordance with national standard.
Description
Technical field
The present invention relates to field of compound material, particularly relate to a kind of nano composite material and preparation method thereof and application.
Background technology
The elimination of impurity is the importance that concerns people's lives in the water.Heavy metal ion such as arsenic are contained in quite a lot of area in China in the underground water, have a strong impact on the people's life and health.The heavy metal ion of eliminating in the water by absorption can be drinkable water with the water resource purification that is unsuitable for drinking.Safe in utilization, cost is low, eliminate the high material of heavy metal ion efficient and have broad application prospects.Up to now, there has been multiple material to be used to eliminate heavy metal ion in the water.
The method of existing water treatment can be divided into two classes, and the one, intermediate processing to be insoluble in the compound form precipitate and separate of water, is applicable to the processing that contains the higher water of concentration of heavy metal ion with heavy metal ion in the water; Another kind of is adsorption method, but this method adsorption efficiency is lower.
Summary of the invention
The purpose of this invention is to provide a kind of nano composite material and preparation method thereof and application.
The method for preparing nano composite material provided by the invention comprises the steps:
The solution uniform load of metal oxide precursor in the surface and duct of porous material, is converted into corresponding metal oxide by in-situ chemical reaction with metal oxide precursor, obtains described nano composite material.
In this method, described metal oxide precursor is nitrate, sulfate, chloride or the acetate of any one metallic element in iron, cobalt, tin, titanium, zinc and the cerium; Described porous material is selected from least a in silica gel, active carbon, kaolin, molecular sieve and the aluminium oxide; In the solution of described metal oxide precursor, solvent is selected from least a in water, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol and the glycerine.
The concentration of described metal oxide precursor solution is 1-65wt%, preferred 30-50%; The ratio of quality and the number of copies of described metal oxide precursor and described porous material is 1: 2-4.
In this method, the method for in-situ chemical reaction is following method a or method b;
Method a: adding the pH value in the reaction system of metal oxide precursor and porous material composition is the alkaline solution of 9-14, carries out in-situ chemical reaction;
Method b: under 150-800 ℃ condition, the reaction system of metal oxide precursor and porous material composition is carried out in-situ chemical reaction.
Among the method a, reaction temperature is 20-80 ℃, and the reaction time is 1-30 minute, preferred 10-20 minute; The concentration of described alkaline solution is 5-40wt%; Alkaline solution is selected from least a in the aqueous solution of the aqueous solution of the aqueous solution, ethamine of ammoniacal liquor, methylamine and ethylenediamine;
Among the method b, the reaction time is 30-720 minute, and the preferred 200-300 of reaction temperature ℃, reaction atmosphere is that vacuum is atmospheric inert atmosphere of 0-1.0 or air atmosphere, preferred 1.0 atmospheric air atmosphere.
After above-mentioned in-situ chemical reaction finished, the method for available washing or calcination was except that other chemical substance residual in the dereaction or that produce.
The application in preparation material for water treatment especially heavy metal (as in mercury, arsenic and the cadmium at least a) sorbing material of the nano composite material for preparing according to the method described above and this material also belongs to protection scope of the present invention.
The present invention utilizes the pore passage structure and the Large ratio surface of porous material, with the even appendix of nano material of metal oxide at porous material surface.This method technology is simple, safety, cost are low, be suitable for large-scale production, the toxicity of solvent is little in the reaction system, environmental pollution is little, preparation gained composite nano materials can be used for adsorbing the heavy metal ion of eliminating in the water, remarkably productive, thus the water resource that will be unsuitable for drinking is purified to meeting the drinkable water of national standard.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples; All solution concentrations are mass percent concentration among the present invention's (comprising following embodiment).
Embodiment 1,
One, preparation nano composite material
Take by weighing the analytically pure nine water ferric nitrates of 250g, be dissolved in the 600mL water, obtain nine water iron nitrate aqueous solutions.Take by weighing 1Kg active carbon (available from chemical reagents corporation of traditional Chinese medicines group), this iron nitrate solution is slowly dripped and constantly mixes, finally add the above-mentioned iron nitrate solution of 1000mL, leave standstill the active carbon that isolated by filtration after a period of time obtains containing the molysite precursor.It is heated 12h under 300 ℃ of following air, make ferric nitrate decompose the active carbon that obtains the load iron oxide.
Two, water treatment test
The sewage different with two heavy metal species ion concentrations carry out the water treatment test according to following method.
1、
Absorbent charcoal material 200 grams of above-mentioned load iron oxide are loaded in the glass tube of 6 centimetres of diameters, are prepared into Filter column.Then 1000 milliliters of mercury ion aqueous solution that contain 1.0mg/L concentration are evenly flow through Filter column with 2 liters/hour flow velocity.By the ion concentration of mercury in the water of Filter column, test triplicate with the elemental analyser analysis, the ion concentration of mercury mean value after obtaining handling is 0.005mg/L.
2、
Absorbent charcoal material 200 grams of above-mentioned load iron oxide are loaded in the glass tube of 6 centimetres of diameters, are prepared into Filter column.Then 2000 milliliters of arsenic ion aqueous solution that contain 10mg/L concentration are evenly flow through Filter column with 4 liters/hour flow velocity.By the arsenic ion concentration in the water of Filter column, test triplicate with the elemental analyser analysis, the ion concentration of mercury mean value after obtaining handling is 0.5mg/L.
Embodiment 2,
One, preparation nano composite material
Take by weighing the analytically pure nine water ferric nitrates of 50g, be dissolved in the 600mL water, obtain nine water iron nitrate aqueous solutions.Take by weighing 1Kg active carbon (available from chemical reagents corporation of traditional Chinese medicines group), this iron nitrate solution is slowly dripped and constantly mixes, finally add the above-mentioned iron nitrate solution of 1000mL, leave standstill the active carbon that isolated by filtration after a period of time obtains containing the molysite precursor.Under the condition of logical nitrogen, 500 ℃ of heating 6h make ferric nitrate decompose the active carbon that obtains the load iron oxide fully with it.
Two, water treatment test
Absorbent charcoal material 200 grams of above-mentioned load iron oxide are loaded in the glass tube of 6 centimetres of diameters, are prepared as Filter column.Then 1000 milliliters of mercury ion aqueous solution that contain 1.0mg/L concentration are evenly flow through Filter column with 2 liters/hour flow velocity.By the ion concentration of mercury in the water of Filter column, test triplicate with the elemental analyser analysis, the ion concentration of mercury mean value after obtaining handling is 0.01mg/L.
Embodiment 3,
One, preparation nano composite material
The ammoniacal liquor that adds 200mL 25% in the active carbon that contains the molysite precursor in embodiment 1 fully stirred 10 minutes in normal temperature (15-30 ℃), filtered and washed 6 times, and it is dried in 80 ℃ of following air.
Two, water treatment test
Absorbent charcoal material 200 grams of above-mentioned load iron oxide are loaded in the glass tube of 6 centimetres of diameters, are prepared as Filter column.Then 2000 milliliters of arsenic ion aqueous solution that contain 0.2mg/L concentration are evenly flow through Filter column with 4 liters/hour flow velocity.By the arsenic ion concentration in the water of Filter column, test triplicate with the elemental analyser analysis, the arsenic ion concentration mean value after obtaining handling is 0.001mg/L, meets national drinking water standard.
Embodiment 4,
One, preparation nano composite material
The methylamine solution that adds 200mL 25% in the active carbon that contains the molysite precursor in embodiment 1 fully stirred 30 minutes in normal temperature (10-20 ℃), filtered and washed 5 times, and it is dried in 250 ℃ of following air.
Two, water treatment test
Absorbent charcoal material 200 grams of above-mentioned load iron oxide are loaded in the glass tube of 6 centimetres of diameters, are prepared as Filter column.Then 1000 milliliters of mercury ion aqueous solution that contain 1.0mg/L concentration are evenly flow through Filter column with 2 liters/hour flow velocity.By the ion concentration of mercury in the water of Filter column, test triplicate with the elemental analyser analysis, the ion concentration of mercury mean value after obtaining handling is 0.05mg/L.
Embodiment 5,
One, preparation nano composite material
Take by weighing 500g and analyze pure iron chloride, be dissolved in the 300mL water, obtain ferric chloride in aqueous solution.Take by weighing 1Kg silica gel (available from Beijing chemical reagents corporation), ferric chloride solution is slowly dripped and constantly mixes, finally add 1000mL solution, leave standstill the silica gel that isolated by filtration after a period of time obtains containing the molysite precursor.The ammoniacal liquor that adds 200mL 25% in the silica gel that contains the molysite precursor fully stirred 15 minutes in normal temperature (15-30 ℃), filtered and washed repeatedly, and it is dried in 80 ℃ of following air.
Two, water treatment test
Silica gel material 160 grams of above-mentioned load iron oxide are loaded in the glass tube of 6 centimetres of diameters, are prepared as Filter column.Then 1000 milliliters of arsenic ion aqueous solution that contain 0.2mg/L concentration are evenly flow through Filter column with 2 liters/hour flow velocity.By the arsenic ion concentration in the water of Filter column, test triplicate with the elemental analyser analysis, the arsenic ion concentration mean value after obtaining handling is 0.005mg/L, meets national drinking water standard.
Embodiment 6,
One, preparation nano composite material
Take by weighing 200g analytical pure sulfuric acid iron, be dissolved in the 300mL water, obtain ferric sulfate aqueous solution.Take by weighing 500g aluminium oxide (available from Beijing chemical reagents corporation), ferrum sulfuricum oxydatum solutum is slowly dripped and constantly mixes, finally add 500mL solution, leave standstill the aluminium oxide that isolated by filtration after a period of time obtains containing the molysite precursor.The ammoniacal liquor that adds 500mL 25% in the aluminium oxide that contains the molysite precursor fully stirs, and filters and washes repeatedly, and it is dried in 80 ℃ of following air.
Two, water treatment test
Alumina material 160 grams of above-mentioned load iron oxide are loaded in the glass tube of 6 centimetres of diameters, are prepared as Filter column.Then 1000 milliliters of cadmium ion aqueous solution that contain 0.2mg/L concentration are evenly flow through Filter column with 1 liter/hour flow velocity.By the concentration of cadmium ions in the water of Filter column, test triplicate with the elemental analyser analysis, the concentration of cadmium ions mean value after obtaining handling is 0.005mg/L.
Embodiment 7,
One, preparation nano composite material
Take by weighing 500g and analyze pure six water cerous nitrates, be dissolved in the 300mL water, obtain the cerous nitrate aqueous solution.Take by weighing 1Kg silica gel, cerous nitrate solution is slowly dripped and constantly mixes, finally add 1000mL solution, leave standstill the silica gel that isolated by filtration after a period of time obtains containing cerium salt precursor.It is heated 12h under 250 ℃ of following air, obtain the silica gel of load cerium oxide.
Two, water treatment test
Silica gel material 160 grams of above-mentioned load cerium oxide are loaded in the glass tube of 6 centimetres of diameters, are prepared as Filter column.Then 1000 milliliters of arsenic ion aqueous solution that contain 0.2mg/L concentration are evenly flow through Filter column with 2 liters/hour flow velocity.By the arsenic ion concentration in the water of Filter column, test triplicate with the elemental analyser analysis, the arsenic ion concentration mean value after obtaining handling is 0.01mg/L.
Claims (7)
1. a method for preparing nano composite material comprises the steps:
The solution uniform load of metal oxide precursor in the surface and duct of porous material, is converted into corresponding metal oxide by in-situ chemical reaction with metal oxide precursor, obtains described nano composite material;
Described metal oxide precursor is nitrate, sulfate, chloride or the acetate of any one metallic element in iron, cobalt and the cerium, and nitrate, chloride or the acetate of any one metallic element in tin, titanium and the zinc;
Described porous material is selected from least a in silica gel, active carbon, kaolin and the molecular sieve;
In the solution of described metal oxide precursor, solvent is selected from least a in water, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol and the glycerine;
The concentration of the solution of described metal oxide precursor is 1-65wt%; The ratio of quality and the number of copies of described metal oxide precursor and described porous material is (1: 2)-(1: 4); The pore volume of porous material is 0.2-0.8ml/g, and specific area is 100-1500m
2/ g;
The method of described in-situ chemical reaction is following method a or method b;
Method a: adding the pH value in the reaction system of metal oxide precursor and porous material composition is the alkaline solution of 9-14, carries out in-situ chemical reaction;
Method b: under 150-800 ℃ condition, the reaction system of metal oxide precursor and porous material composition is carried out in-situ chemical reaction.
2. method according to claim 1 is characterized in that: among the described method a, reaction temperature is 20-80 ℃; Reaction time is 1-30 minute; The concentration of described alkaline solution is 5-40wt%;
Among the described method b, the reaction time is 30-720 minute; Reaction atmosphere is that vacuum is atmospheric inert atmosphere of 0-1.0 or air atmosphere.
3. method according to claim 2 is characterized in that: among the described method a, reaction temperature is 30-50 ℃; Reaction time is 10-20 minute; The concentration of described alkaline solution is 20-30wt%;
Among the described method b, the reaction time is 200-250 minute; Reaction atmosphere is 1.0 atmospheric air atmosphere.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: among the described method a, alkaline solution is selected from least a in the aqueous solution of the aqueous solution of the aqueous solution, ethamine of ammoniacal liquor, methylamine and ethylenediamine;
Among the described method b, reaction temperature is 200-300 ℃.
5. the nano composite material for preparing of the arbitrary described method of claim 1-4.
6. the application of the described nano composite material of claim 5 in the preparation material for water treatment; The described material for water treatment metal-adsorbing material of attaching most importance to.
7. application according to claim 6 is characterized in that: described heavy metal is selected from least a in mercury, arsenic and the cadmium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105001571B (en) * | 2015-07-03 | 2017-11-03 | 北京理工大学 | Metal oxide-loaded activated carbon synergistic expandable flame retardant CABLE MATERIALS and preparation method |
| CN106268617A (en) * | 2016-08-26 | 2017-01-04 | 中国科学院合肥物质科学研究院 | Fe2O3 doping manganese dioxide micro-nano structure material and preparation method and application |
| CN107537437B (en) * | 2017-09-29 | 2020-08-04 | 天津大学 | Supported bi-component nano oxide adsorbent, preparation method and application thereof |
| CN108854966A (en) * | 2018-07-20 | 2018-11-23 | 张家港市东威新材料技术开发有限公司 | A kind of preparation method of silica gel supported composite adsorbing material |
| CN109603746A (en) * | 2018-12-11 | 2019-04-12 | 中国科学院生态环境研究中心 | Support structures and the preparation method and application thereof for heavy metal contaminants absorption |
| CN111250033B (en) * | 2020-03-11 | 2021-09-03 | 安徽建筑大学 | Metal oxide porous micro-nano hierarchical structure modified honeycomb stone and preparation method and application thereof |
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| CN101010367A (en) * | 2004-07-14 | 2007-08-01 | 新加坡科技研究局 | Nanometer composite material and its preparing method |
| CN101128621A (en) * | 2005-02-24 | 2008-02-20 | 国家科研中心 | Composite material consisting of a porous matrix and metal or metal oxide nanoparticles |
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Patent Citations (4)
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| US6670539B2 (en) * | 2001-05-16 | 2003-12-30 | Delphi Technologies, Inc. | Enhanced thermoelectric power in bismuth nanocomposites |
| CN101010367A (en) * | 2004-07-14 | 2007-08-01 | 新加坡科技研究局 | Nanometer composite material and its preparing method |
| CN101128621A (en) * | 2005-02-24 | 2008-02-20 | 国家科研中心 | Composite material consisting of a porous matrix and metal or metal oxide nanoparticles |
| CN1785502A (en) * | 2005-11-02 | 2006-06-14 | 刘应希 | Nano-composite composite material and its preparation method |
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