CN103143318B - Preparation method for siliceous earth/FeOOH composite materials in micro-nano structure - Google Patents
Preparation method for siliceous earth/FeOOH composite materials in micro-nano structure Download PDFInfo
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- CN103143318B CN103143318B CN201210519590.XA CN201210519590A CN103143318B CN 103143318 B CN103143318 B CN 103143318B CN 201210519590 A CN201210519590 A CN 201210519590A CN 103143318 B CN103143318 B CN 103143318B
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Abstract
The invention discloses a preparation method for siliceous earth/FeOOH composite materials in a micro-nano structure. The preparation method comprises the steps of evenly attaching FeOOH obtained by a water-bath method to the surface of siliceous earth, respectively characterizing prepared products by a field emission scanning electronic microscope and an X-ray diffraction instrument, and knowing that alpha-FeOOH is of an orthorhombic system structure, evenly distributed on the surface of the siliceous earth and even in morphological structure. The alpha-FeOOH of the composite materials is of a nano structure and has higher crystallinity and purity. During a preparation process, due to the fact that substances like templates are not added, follow-up processing is convenient to achieve, reaction temperature is low, reaction time is short, processes are simple, cost is low, and the preparation method is potentially applied to the field of environment.
Description
Technical field
The present invention relates generally to a kind of preparation method with the diatomite/hydroxyl oxidize iron composite material of micro-nano structure, belongs to adsorbent application.
Background technology
In inorganic natural minerals, the biological silicalite that diatomite is made up of the siliceous remains of diatom and other microorganism.Its mineralogical composition is opal (SiO mainly
2h
2and mutation O).Diatomite light weight, porous, relative density are little, many excellent performances such as also there is unique microcellular structure simultaneously, specific area is large, bulk density is little, be acidproof, surface cover by a large amount of silicone hydroxyl, usually its particle surface is with negative electrical charge, therefore, its application pay attention to day by day in wastewater treatment gets up, especially for heavy metal cation pollutant.
Due to diatomite, there is microcellular structure and effectively can remove contained most of impurity with after acid treatment, obtaining stable internal pore structure, a kind of good carrier material can be become.Therefore be a good selection to diatomite modifying metallic oxide, diatomite surface is deposited to by the negative electrical charge absorption after diatomite surface dehydrogenation by the hot method metal cation of aqueous solvent, obtain the composite with micro-/micro-nano structure, this overcome the shortcoming that diatomaceous settling property is low and hydraulic detention time (HRT) is long, the volume requirement of structures is also reduced greatly simultaneously, strengthen the adsorption capacity of heavy metal.In metal oxide, FeOOH has higher charge density on the other hand, compared with bigger serface, distinctive crystal property, therefore heavy metal absorption property is comparatively strong, but easily reunites, and not easily separated.Therefore, after alpha-feooh being assembled into diatomite surface by water-soluble fluorine, playing the effect of the unique microcellular structure of diatomite on the one hand, enriched diatomaceous microcellular structure, improved diatomite character in aqueous; On the other hand because Nano ferric hydroxide is deposited on diatomaceous micropore, prevent the reunion of nano particle, be of value to and increase material surface electric charge and surface area, the absorption property of heavy metal pollutant can be strengthened, reach structure and strengthen characterization of adsorption; Simultaneously because integral composite macro manifestations is micrometer structure, institute is so that composite is separated from solution.Therefore after assembling micro-/composite of receiving gives full play to diatomaceous microcellular structure and surface charge effect, strengthens structure characterization of adsorption.For the advantage taking full advantage of bi-material this composite, both are organically assembled, obtain a kind of green, cheapness, high absorption property and have structure strengthen absorption property micro-/micro-nano structure composite.
Summary of the invention
The object of the invention is just to provide a kind of preparation method with the diatomite/hydroxyl oxidize iron composite material of micro-nano structure.
The present invention is achieved by the following technical solutions:
There is a preparation method for the diatomite/hydroxyl oxidize iron composite material of micro-nano structure, it is characterized in that comprising the following steps:
(1) take a certain amount of diatomite, join in 2-4M hydrochloric acid solution, be heated to 90-95
oc, and after carrying out mechanical agitation 20-25h, be neutral with deionized water and absolute ethyl alcohol cyclic washing to the aqueous solution, suction filtration is also dried stand-by;
(2) by deionized water and ethylene glycol according to the proportions of 0.8 ~ 1.2:0.8 ~ 1.2 and ultrasonic 5-10 minute, be then divided into two parts and be respectively charged in size two volumetric flasks;
(3) in Large Copacity bottle, FeSO is added
47H
2diatomite after O and step (1) process, adds urea in low capacity bottle, then distinguishes ultrasonic 5-15 minute; Described diatomite, FeSO
47H
2the mass ratio of O and urea is 2-5:1:1-1.5; Diatomite and ionized water and ethylene glycol gross mass volume ratio are 1g:15-30mL;
(4) pour in there-necked flask by the mixture in Large Copacity bottle, being put into temperature is 90-95
oin C Water Tank with Temp.-controlled, carry out stirring 5-15 minute;
(5) by peristaltic pump, the solution in low capacity bottle is injected above-mentioned there-necked flask with 0.8-1.1mL/min speed, treat that in low capacity bottle, solution injects complete, changes speed into 2.8-3mL/min, is passed into by air in above-mentioned there-necked flask;
(6) after 3-4 hour, take out product, be neutral with deionized water and absolute ethyl alcohol cyclic washing to the aqueous solution, finally the centrifugal precipitation obtained dried in an oven, obtain the compound of diatomite/FeOOH.
Advantage of the present invention is:
(1) alpha-feooh that immersion method obtains is attached to diatomite surface uniformly, field emission scanning electron microscope and x-ray diffractometer is used to characterize respectively obtained product, known alpha-feooh is orthorhombic structure, be evenly distributed in diatomite surface and pattern is homogeneous;
(2) alpha-feooh of above-mentioned composite presents nanostructured, has higher crystallinity and higher purity;
(3) the method is in preparation process, owing to not adding the materials such as template, makes subsequent treatment convenient, and reaction temperature is low, the time is short, technique is simple, cheap;
(4) the preparation process environmental protection of the method, does not use any poisonous and hazardous source of iron.
(5) whole course of reaction is controlled by peristaltic pump, realizes accurate, Automated condtrol; Select urea as precipitating reagent simultaneously, and slowly inject copperas solution by peristaltic pump, slowly decompose, control pH value uniformity in solution, prevent hydroxyl excessive concentration from causing product to reunite simultaneously.This process synergic dispersant ethylene glycol is the important guarantee controlling alpha-feooh appearance and size homogeneity, can ensure the growth of alpha-feooh at diatomite surface uniform simultaneously.
Accompanying drawing explanation
Fig. 1 takes to after diatomite/alpha-feooh scanning electronic microscope observation the photo obtained, the diatomite that Fig. 1 (a) is unmodified, Fig. 1 (b) ~ (d) is the diatomite after modification, as seen from Figure 1, prepare alpha-feooh in the diatomite/alpha-feooh composite with micro-nano structure be needle-shaped nano-structure and be evenly distributed in diatomite surface.
Fig. 2 observes outside de-carbon by X-ray electron spectrum, and remaining only have iron, oxygen and silicon (because instrument reason hydrogen cannot detect), shows that the main component of this composite is silicon, iron, oxygen, so this product has higher degree by table one.
Fig. 3 is XRD spectra Fig. 1 Phlips X ' Pert type X-ray diffraction instrument being recorded to composite, from XRD spectra, at composite except diatomite characteristic peak, also there is the characteristic peak of obvious FeOOH; Can find out in composite except diatomite characteristic peak also there is the characteristic peak of FeOOH equally by infrared, therefore products therefrom is diatomite/alpha-feooh compound.
Fig. 4 carries out thermogravimetric analysis to synthesized sample; By Fig. 4 a known through diatomite modify before without obvious characteristic peak; From Fig. 4 b, 246 after modification
othere is comparatively significantly characteristic peak near C, this peak produces mainly due to the FeOOH after modification, illustrates that alpha-feooh is present in composite by the above results.
Fig. 5 carries out specific surface and heavy metal adsorption to the iron carbonyl in Fig. 1, and the specific surface that Fig. 5 a records institute's diatomite/alpha-feooh composite by nitrogen adsorption and desorption is 90.3m
2/ g, than front 51.9 m of modification
2/ g is greatly improved; Langmuir equation is met by the adsorption process of the known composite of Fig. 5 b (oxalic acid modification) heavy metal lead, and the diatomite (adsorbance is 210.1 mg/g) after modifying is significantly improved relative to (165.6 mg/g) adsorbance tool before modification, illustrate that it is in environmental improvement,, there is potential application in especially heavy metal absorption aspect.
detailed description of the invention
Embodiment 1
There is a preparation method for the diatomite/hydroxyl oxidize iron composite material of micro-nano structure, comprise the following steps:
(1) first take the former diatomite of 10g, add in 150ml 2M hydrochloric acid solution, be transferred in the there-necked flask of 250ml, heating water bath to 90
oc also, after stirring 24h, cleans until solution is in neutral, suction filtration drying repeatedly with deionized water and ethanol.
(2) first the deionized water of 60ml and 60ml ethylene glycol are evenly mixed in the volumetric flask of 250ml, then get the volumetric flask that 90ml injects 250ml, and take 1.98 grams of FeSO
47H
2o, the diatomite after 5 grams of cleanings adds in volumetric flask, ultrasonic 5 minutes;
(3) deionized water of remaining 30ml and ethylene glycol mixture are injected in the conical flask of 50ml, then add 1.5 grams of urea and ultrasonic 10 minutes;
(4) Water Tank with Temp.-controlled temperature is set to 90 degrees Celsius, after temperature arrives 90 degrees Celsius, ferrous sulfate and diatomite mixed solution is poured in the there-necked flask of 250ml and to be put in Water Tank with Temp.-controlled, carrying out stirring 5 minutes;
After (5) 5 minutes, with the speed of 1ml/min, urea liquid is squeezed in there-necked flask by peristaltic pump; Treat that urea liquid input is complete, change peristaltic pump speed into 3ml/min and pass into air in solution;
After (6) 3 hours, close peristaltic pump and stop heating, take out reactant and repeatedly to clean with deionized water and ethanol until solution is in neutrality, finally by centrifugal obtain be deposited in vacuum drying chamber and dry, obtain diatomite/hydroxyl oxidize iron complexes, pattern as shown in Figure 1.
Embodiment 2
(1) first take the former diatomite of 10g, add in 150ml 2M hydrochloric acid solution, be transferred in the there-necked flask of 250ml, heating water bath to 90
oc also, after stirring 24h, cleans until solution is in neutral, suction filtration drying repeatedly with deionized water and ethanol;
(2) first the deionized water of 60ml and 60ml ethylene glycol are evenly mixed in the volumetric flask of 250ml, then get the volumetric flask that 90ml injects 250ml, and take 0.99 gram of FeSO
47H
2o, the diatomite after 5 grams of cleanings adds in volumetric flask, ultrasonic 5 minutes;
(3) deionized water of remaining 30ml and ethylene glycol mixture are injected in the conical flask of 50ml, then add 0.75 gram of urea and ultrasonic 10 minutes;
(4) Water Tank with Temp.-controlled temperature is set to 95
oc, treats that temperature arrives 95
oafter C, ferrous sulfate and diatomite mixed solution to be poured in the there-necked flask of 250ml and to be put in Water Tank with Temp.-controlled, carrying out stirring 5 minutes;
After (5) 5 minutes, with the speed of 1ml/min, urea liquid is squeezed in there-necked flask by peristaltic pump; Treat that urea liquid input is complete, change peristaltic pump speed into 3ml/min and pass into air in solution;
After (6) 3 hours, close peristaltic pump and stop heating, take out reactant and repeatedly to clean with deionized water and ethanol until solution is in neutrality, finally by centrifugal obtain be deposited in vacuum drying chamber and dry, obtain diatomite/hydroxyl oxidize iron complexes, pattern as shown in Figure 1.
Claims (1)
1. there is a preparation method for the diatomite/hydroxyl oxidize iron composite material of micro-nano structure, it is characterized in that comprising the following steps:
(1) take a certain amount of diatomite, join in 2-4M hydrochloric acid solution, be heated to 90-95
oc, and after carrying out mechanical agitation 20-25h, be neutral with deionized water and absolute ethyl alcohol cyclic washing to the aqueous solution, suction filtration is also dried stand-by;
(2) by deionized water and ethylene glycol according to the proportions of 0.8 ~ 1.2:0.8 ~ 1.2 and ultrasonic 5-10 minute, be then divided into two parts and be respectively charged in size two volumetric flasks;
(3) in Large Copacity bottle, FeSO is added
47H
2diatomite after O and step (1) process, adds urea in low capacity bottle, then distinguishes ultrasonic 5-15 minute; Described diatomite, FeSO
47H
2the mass ratio of O and urea is 2-5:1:1-1.5; Diatomite and ionized water and ethylene glycol gross mass volume ratio are 1g:15-30mL;
(4) pour in there-necked flask by the mixture in Large Copacity bottle, being put into temperature is 90-95
oin C Water Tank with Temp.-controlled, carry out stirring 5-15 minute;
(5) by peristaltic pump, the solution in low capacity bottle is injected above-mentioned there-necked flask with 0.8-1.1mL/min speed, treat that in low capacity bottle, solution injects complete, changes speed into 2.8-3mL/min, is passed into by air in above-mentioned there-necked flask;
(6) after 3-4 hour, take out product, be neutral with deionized water and absolute ethyl alcohol cyclic washing to the aqueous solution, finally the centrifugal precipitation obtained dried in an oven, obtain the diatomite/hydroxyl oxidize iron complexes with micro-nano structure.
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| CN103846075A (en) * | 2013-12-22 | 2014-06-11 | 北京工业大学 | Preparation method for alpha-Fe2O3 nano wire chemically-modified kieselguhr adsorbent |
| CN105582883B (en) * | 2015-12-25 | 2017-12-15 | 北海开元生物科技有限公司 | A kind of activated diatomaceous earth and the application in blood product production |
| CN106521461B (en) * | 2016-12-02 | 2018-08-14 | 岳衡 | A kind of preparation method of FeOOH film |
| CN108410596B (en) * | 2018-05-08 | 2020-04-07 | 福州秘庄日化有限公司 | Multifunctional laundry detergent and preparation process thereof |
| CN110743491A (en) * | 2019-10-11 | 2020-02-04 | 江苏理工学院 | Preparation method and application of α -FeOOH @ diatomite composite material |
| CN110975798B (en) * | 2019-11-13 | 2021-07-02 | 浙江大学 | Preparation method, application and regeneration method of FeO (OH) -diatomite composite adsorbent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101584962A (en) * | 2008-05-23 | 2009-11-25 | 北京三聚环保新材料股份有限公司 | High-strength FeOOH desulfurizer and preparation method thereof |
| CN102091591A (en) * | 2010-12-29 | 2011-06-15 | 广东工业大学 | Kieselguhr modified adsorption material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101584962A (en) * | 2008-05-23 | 2009-11-25 | 北京三聚环保新材料股份有限公司 | High-strength FeOOH desulfurizer and preparation method thereof |
| CN102091591A (en) * | 2010-12-29 | 2011-06-15 | 广东工业大学 | Kieselguhr modified adsorption material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
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| 硅藻土负载羟基氧化铁的制备及除磷性能研究;姚煌等;《无机盐工业》;20110531;第43卷(第05期);24-27 * |
| 羟基氧化铁改性硅藻土对六价铬的吸附性能;路则栋等;《地下水》;20121231;第34卷(第6期);180-183 * |
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