CN103846075A - Preparation method for alpha-Fe2O3 nano wire chemically-modified kieselguhr adsorbent - Google Patents

Preparation method for alpha-Fe2O3 nano wire chemically-modified kieselguhr adsorbent Download PDF

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CN103846075A
CN103846075A CN201310714899.9A CN201310714899A CN103846075A CN 103846075 A CN103846075 A CN 103846075A CN 201310714899 A CN201310714899 A CN 201310714899A CN 103846075 A CN103846075 A CN 103846075A
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preparation
suspension
diatomite
solution
fecl
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杜玉成
郑广伟
孙广兵
张黎明
任象玉
李志辉
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Beijing University of Technology
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Beijing University of Technology
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Abstract

The invention discloses a preparation method for an alpha-Fe2O3 nano wire chemically-modified kieselguhr adsorbent and relates to the field of materials. The preparation method comprises the steps of dissolving 20 grams of kieselguhr in 50ml of distilled water, adjusting the pH into 3.0-5.0 through hydrochloric acid, and stirring in a constant-temperature water bath at the temperature of 40-60 DEG C for half an hour to prepare a kieselguhr suspension; respectively and simultaneously dripping 20ml of a prepared FeCl3 solution and a 10wt% urea solution into the kieselguhr suspension in a three-necked bottle, wherein the FeCl3 solution and the urea solution have different concentrations; in the dripping process, adjusting the dripping amount of the urea solution to keep the pH value of the suspension to be constant; after the dripping of the FeCl3 is finished, stirring for reaction under constant temperature for 30 hours, performing aging, suction filtration and washing to obtain a precursor, drying the precursor at the temperature of 80 DEG C, finally heating to 500 DEG C for thermal treatment at the heating rate of 5 DEG C per hour, and preserving the heat for 1 hour. The maximum adsorption quantities of a composite adsorption material prepared by adopting the preparation method disclosed by the invention to As(III) and As(V) are respectively 60.65mg/g and 81.16mg/g.

Description

A kind of α-Fe 2o 3the preparation method of nano wire chemical modification diatomite adsorbant
Technical field
The present invention relates to Material Field, is a kind of α-Fe 2o 3the preparation method of nano wire chemical modification diatomite adsorbant.
Background technology
Being classified as in the heavy metal contaminants of keypoint treatment by country, because chromium, arsenic present negative valency state in water body, there is (CrO with acid radical anion 4 2-, Cr 2o 7 2-; H 2asO 3 -, HasO 3 2-, AsO 3 3-; H 2asO 4 -, HAsO 4 2-, AsO 4 3-), and chromium, the safe threshold values of arsenic very low (0.04mg/L, 0.01mg/g), the most difficult improvement up to standard.The method of processing chromium, arsenic waste water has: oxidizing process, flocculation sedimentation, membrane separation process, absorption method etc.Absorption method (especially chemiadsorption) simple and convenient, efficient, low cost, be applicable to the deep purifying of low concentration containing chromium, arsenic waste water, and easy industrial applications, is acknowledged as one of approach of the most effectively processing containing heavy metal ion sewage such as chromium, arsenic.But absorption method, in application process, is mainly limited to the adsorption (adsorption capacity, adsorption rate) of sorbing material, and therefore, the adsorption that how to improve sorbing material is very crucial.Research shows to have bigger serface and the porous material that enriches surface functional group, is the excellent adsorbent for heavy metal such as chromium, arsenic; With respect to traditional adsorbent, nano structural material has abundant surface-active functional group and compared with bigger serface, and more efficient as chromium, arsenate Anion-adsorption, its research also receives much concern.But nano particle adsorbent, exists particle agglomeration (affecting adsorption) and adsorbent to be difficult to the problems such as subsequent treatment (Separation of Solid and Liquid difficulty).Nanostructured or nano particle metal oxide (oxyhydroxide) carry out compound addressing the above problem with large scale matrix material, as coated in iron activated carbon, iron oxide and carbon fiber compound etc., but these materials, because cost is high, have limited it greatly in industrial application.Therefore, cheap, absorption property is excellent, be convenient to same water body separates, thus it is extremely important to meet the sorbing material preparation research of requirement on industrial application.Therefore, the preparation of nanostructured metal oxides and large scale base composite absorbent, extremely important for the actual treatment of heavy metal ion-containing waste water cheaply.
Diatomite is a kind of inorganic mineral material with natural micropore structure, and small aperture is that 20～50nm, macropore diameter are 100～300nm, and main chemical is amorphous Si O 2,, in network, there is coordination defect and oxo bridge defect in the network structure being formed by the mutual bridging of silicon-oxy tetrahedron.Upper at surperficial Si-O-" dangling bonds ", easily form Si-OH in conjunction with H, in water, be easily dissociated into Si-O -and H +, make diatomite surface present elecrtonegativity.Therefore, kieselguhr adsorption heavy metal cation, has natural structural advantage.Due to the natural sex of diatomite microcellular structure, make significantly to reduce and process heavy metal ion adsorbing material and prepare expense and become possibility.But diatomite is to Heavy Metals in Waters acid radical anion (H 2asO 3 -, HasO 3 2-, AsO 3 3-; H 2asO 4 -, HAsO 4 2-, AsO 4 3-; .CrO 4 2-, Cr 2o 7 2-) clearance is low.Need to carry out surface modification to diatomite as adsorbent, but up to the present, surface recombination modified to diatomite, all showing as modifier mixes with diatomaceous mechanicalness, be unfavorable for the absorption of modification infusorial earth to heavy metal ion and with the separating of water body, therefore, the preparation of micro-nanometer ordered structure metal oxide modified diatomite adsorbant is very meaningful.
Summary of the invention
The object of the invention is to carry out α-Fe for diatomite 2o 3nanowire surface chemistry is modified, and the most cost of existing natural and artificial synthetic porous adsorbent is high, and the adsorbent of nanostructured exists again the problem that is not easy to carry out Separation of Solid and Liquid, provides on a kind of diatomite algae dish and deposits α-Fe 2o 3the absorbent preparation method of nano wire.The method production cost is low, and operating procedure is simple, is easy to suitability for industrialized production.
Diatom base deposition α-Fe provided by the present invention 2o 3nano wire adsorbent is by diatomite, crystallization ferric trichloride, urea, and hydrochloric acid, NaOH, water, employing coprecipitation are synthesized.
A kind of α-Fe provided by the present invention 2o 3the preparation method of nano wire chemical modification diatomite adsorbant, is characterized in that, comprises the following steps:
The first step, takes 20g diatomite and is dissolved in 50ml distilled water, with salt acid for adjusting pH be 3.0～5.0, in 40～60 DEG C of thermostatted water bathing pools, stir half an hour, prepare diatomite suspension; Put into the three-necked bottle with condensing unit, and three-necked bottle is placed in to sea water bath 40-60 DEG C of constant temperature stirring;
Second step, takes a certain amount of crystallization ferric trichloride and is dissolved in the water, the FeCl that preparation quality percent concentration is 6-12% 3solution, stand-by;
The 3rd step, takes a certain amount of urea and is dissolved in distilled water, and the urea liquid that preparation quality concentration is 10% is stand-by;
The 4th step, will prepare the FeCl of variable concentrations 3solution 20ml and 10wt% urea liquid splash into respectively in the diatomite suspension of three-necked bottle simultaneously; In dropping process, regulate the amount of splashing into of urea liquid, the pH value of suspension is remained unchanged;
The 5th step, FeCl 3after solution drips, constant temperature stirring reaction 30h, after ageing, suction filtration, washing by obtained presoma 80 DEG C dry, be finally warming up to 500 DEG C and heat-treat, heating rate 5, DEG C/temperature retention time is 1h.
The present invention adopts chemical coprecipitation to pass through depositing nano structure α-Fe on diatom soil matrix core 2o 3nano wire, prepare and there is nanostructured metal oxides and the compound high-efficiency adsorbent of large scale matrix material, by adopting this process gained composite adsorbing material to be respectively the maximal absorptive capacity of As (III) and As (V): 60.65mg/g, 81.16mg/g.
Brief description of the drawings
The X-ray diffraction curve of Fig. 1 embodiment 1,2 product and diatomite original soil
Fig. 2 A is one of diatomaceous scanning electron microscope image
Fig. 2 C is two of diatomaceous scanning electron microscope image
Fig. 2 B is one of scanning electron microscope image of embodiment 2 products
Fig. 2 D be embodiment 2 products scanning electron microscope image two
Fig. 3 A is diatomaceous TEM picture
Fig. 3 B is the TEM figure of embodiment 3 products
Fig. 3 C is the HRTEM figure of embodiment 3 products
The saturated adsorption curve of Fig. 4 embodiment 4 products to As (III) and As (V)
The adsorption desorption curve of Fig. 5 embodiment 5 products and diatomite original soil
Fig. 6 embodiment 5 products and diatomite original soil pore size distribution curve
Detailed description of the invention
Embodiment 1
The first step, takes 20g diatomite and is dissolved in 50ml distilled water, with salt acid for adjusting pH be 3.0, in 50 DEG C of thermostatted water bathing pools, stir half an hour, prepare diatomite suspension.Put into condensing unit three-necked bottle, and three-necked bottle is placed in to sea water bath constant temperature (50 DEG C) stirring.
Second step, takes a certain amount of crystallization ferric trichloride and is dissolved in the water, the FeCl that preparation quality percent concentration is 6% 3solution, stand-by.
The 3rd step, takes a certain amount of urea and is dissolved in distilled water, and the urea liquid that preparation quality concentration is 10% is stand-by.
The 4th step is 6% FeCl by preparing concentration 3solution 20ml and 10wt% urea liquid splash into respectively in the diatomite suspension of three-necked bottle simultaneously.In dropping process, regulate the amount of splashing into of urea liquid, the pH value of suspension is remained unchanged.
The 5th step, FeCl 3after solution drips, constant temperature stirring reaction 30h is dry at 80 DEG C by obtained product after ageing, suction filtration, washing.
Embodiment 2
The first step, takes 20g diatomite and is dissolved in 50ml distilled water, with salt acid for adjusting pH be 3.5, in 40 DEG C of thermostatted water bathing pools, stir half an hour, prepare diatomite suspension.Put into the three-necked bottle with condensing unit, and three-necked bottle is placed in to sea water bath constant temperature (50 DEG C) stirring.
Second step, takes a certain amount of crystallization ferric trichloride and is dissolved in the water, the FeCl that preparation quality percent concentration is 6% 3solution, stand-by.
The 3rd step, takes a certain amount of urea and is dissolved in distilled water, and the urea liquid that preparation quality concentration is 10% is stand-by.
The 4th step is 6% FeCl by preparing concentration 3solution 20ml and 10wt% urea liquid splash into respectively in the diatomite suspension of three-necked bottle simultaneously.In dropping process, regulate the amount of splashing into of urea liquid, the pH value of suspension is remained unchanged.
The 5th step, FeCl 3after solution drips, constant temperature stirring reaction 30h, after ageing, suction filtration, washing by obtained presoma 80 DEG C dry, be finally placed in electric furnace and heat-treat in 500 DEG C, 5 DEG C/min of heating rate, temperature retention time are 1h.
Embodiment 3
The first step, takes 20g diatomite original soil and is dissolved in 50ml distilled water, with salt acid for adjusting pH be 4, in 60 DEG C of thermostatted water bathing pools, stir half an hour, prepare diatomite suspension.Put into the three-necked bottle with condensing unit, and three-necked bottle is placed in to sea water bath constant temperature (40 DEG C) stirring.
Second step, takes a certain amount of crystallization ferric trichloride and is dissolved in the water, the FeCl that preparation quality percent concentration is 8% 3solution, stand-by.
The 3rd step, takes a certain amount of urea and is dissolved in distilled water, and the urea liquid that preparation quality concentration is 10% is stand-by.
The 4th step is 8% FeCl by preparing concentration 3solution 20ml and 10wt% urea liquid splash into respectively in the diatomite suspension of three-necked bottle simultaneously.In dropping process, regulate the amount of splashing into of urea liquid, the pH value of suspension is remained unchanged.
The 5th step, FeCl 3after solution drips, constant temperature stirring reaction 30h, after ageing, suction filtration, washing by obtained presoma 80 DEG C dry, be finally placed in electric furnace and heat-treat in 500 DEG C, 5 DEG C/min of heating rate, temperature retention time are 1h.
Embodiment 4
The first step, takes 20g diatomite original soil and is dissolved in 50ml distilled water, with salt acid for adjusting pH be 4.5, in 60 DEG C of thermostatted water bathing pools, stir half an hour, prepare diatomite suspension.Put into condensing unit three-necked bottle, and three-necked bottle is placed in to sea water bath constant temperature (60 DEG C) stirring.
Second step, takes a certain amount of crystallization ferric trichloride and is dissolved in the water, preparation quality percent concentration is 10%, FeCl 3solution, stand-by.
The 3rd step, takes a certain amount of urea and is dissolved in distilled water, and the urea liquid that preparation quality concentration is 10% is stand-by.
The 4th step is 10% FeCl by preparing concentration 3solution 20ml and 10wt% urea liquid splash into respectively in the diatomite suspension of three-necked bottle simultaneously.In dropping process, regulate the amount of splashing into of urea liquid, the pH value of suspension is remained unchanged.
The 5th step, FeCl 3after solution drips, constant temperature stirring reaction 30h, after ageing, suction filtration, washing by obtained presoma 80 DEG C dry, be finally placed in electric furnace and heat-treat in 500 DEG C, 5 DEG C/min of heating rate, temperature retention time are 1h.
Embodiment 5
The first step, takes 20g diatomite original soil and is dissolved in 50ml distilled water, with salt acid for adjusting pH be 5, in 50 DEG C of thermostatted water bathing pools, stir half an hour, prepare diatomite suspension.Put into the three-necked bottle with condensing unit, and three-necked bottle is placed in to sea water bath constant temperature (40 DEG C) stirring.
Second step, takes a certain amount of crystallization ferric trichloride and is dissolved in the water, the FeCl that preparation quality percent concentration is 12% 3solution, stand-by.
The 3rd step, takes a certain amount of urea and is dissolved in distilled water, and the urea liquid that preparation quality concentration is 10% is stand-by.
The 4th step is 12% FeCl by preparing concentration 3solution 20ml and 10wt% urea liquid splash into respectively in the diatomite suspension of three-necked bottle simultaneously.In dropping process, regulate the amount of splashing into of urea liquid, the pH value of suspension is remained unchanged.
The 5th step, FeCl 3after solution drips, constant temperature stirring reaction 30h, after ageing, suction filtration, washing by obtained presoma 80 DEG C dry, be finally placed in electric furnace and heat-treat in 500 DEG C, 5 DEG C/min of heating rate, temperature retention time are 1h.
Table 1
Maximal absorptive capacity Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
As(III) 48.76 52.17 56.92 59.85 57.38
As(V) 69.63 73.36 76.63 80.47 77.49

Claims (1)

1. a α-Fe 2o 3the preparation method of nano wire chemical modification diatomite adsorbant, is characterized in that, comprises the following steps:
The first step, takes 20g diatomite and is dissolved in 50ml distilled water, with salt acid for adjusting pH be 3.0～5.0, in 40～60 DEG C of thermostatted water bathing pools, stir half an hour, prepare diatomite suspension; Put into the three-necked bottle with condensing unit, and three-necked bottle is placed in to sea water bath 40-60 DEG C of constant temperature stirring;
Second step, takes a certain amount of crystallization ferric trichloride and is dissolved in the water, the FeCl that preparation quality percent concentration is 6-12% 3solution, stand-by;
The 3rd step, takes a certain amount of urea and is dissolved in distilled water, and the urea liquid that preparation quality concentration is 10% is stand-by;
The 4th step, will prepare the FeCl of variable concentrations 3solution 20ml and 10wt% urea liquid splash into respectively in the diatomite suspension of three-necked bottle simultaneously; In dropping process, regulate the amount of splashing into of urea liquid, the pH value of suspension is remained unchanged;
The 5th step, FeCl 3after solution drips, constant temperature stirring reaction 30h, after ageing, suction filtration, washing by obtained presoma 80 DEG C dry, be finally warming up to 500 DEG C and heat-treat, heating rate 5, DEG C/temperature retention time is 1h.
CN201310714899.9A 2013-12-22 2013-12-22 Preparation method for alpha-Fe2O3 nano wire chemically-modified kieselguhr adsorbent Pending CN103846075A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106622126A (en) * 2016-12-06 2017-05-10 北京工业大学 Carbon fiber composite material capable of adsorbing and degrading Cr(VI) and preparation method and applications thereof
CN107337825A (en) * 2017-07-31 2017-11-10 常州杰轩纺织科技有限公司 A kind of preparation method of yielding rubber
CN108816178A (en) * 2018-06-07 2018-11-16 暨南大学 A kind of porous ceramic grain and preparation method loading nano-iron oxide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102091591A (en) * 2010-12-29 2011-06-15 广东工业大学 Kieselguhr modified adsorption material and preparation method and application thereof
CN103143318A (en) * 2012-12-06 2013-06-12 中国科学院合肥物质科学研究院 Preparation method for siliceous earth/FeOOH composite materials in micro-nano structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102091591A (en) * 2010-12-29 2011-06-15 广东工业大学 Kieselguhr modified adsorption material and preparation method and application thereof
CN103143318A (en) * 2012-12-06 2013-06-12 中国科学院合肥物质科学研究院 Preparation method for siliceous earth/FeOOH composite materials in micro-nano structure

Non-Patent Citations (1)

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Title
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106622126A (en) * 2016-12-06 2017-05-10 北京工业大学 Carbon fiber composite material capable of adsorbing and degrading Cr(VI) and preparation method and applications thereof
CN106622126B (en) * 2016-12-06 2019-03-22 北京工业大学 Adsorbable degradation Cr (VI) carbon fibre composite of one kind and the preparation method and application thereof
CN107337825A (en) * 2017-07-31 2017-11-10 常州杰轩纺织科技有限公司 A kind of preparation method of yielding rubber
CN107337825B (en) * 2017-07-31 2019-01-01 深圳深凯硅胶制品有限公司 A kind of preparation method of yielding rubber
CN108816178A (en) * 2018-06-07 2018-11-16 暨南大学 A kind of porous ceramic grain and preparation method loading nano-iron oxide

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Application publication date: 20140611