CN104549126A - Nano iron/oyster shell composite material, and preparation method and application thereof - Google Patents
Nano iron/oyster shell composite material, and preparation method and application thereof Download PDFInfo
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- CN104549126A CN104549126A CN201510041880.1A CN201510041880A CN104549126A CN 104549126 A CN104549126 A CN 104549126A CN 201510041880 A CN201510041880 A CN 201510041880A CN 104549126 A CN104549126 A CN 104549126A
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- oyster shell
- iron
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- nanoscale iron
- arsenic
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 182
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 108
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 51
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 239000002689 soil Substances 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- -1 iron ions Chemical class 0.000 claims abstract description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 7
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 9
- 230000010355 oscillation Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 241000237502 Ostreidae Species 0.000 abstract description 4
- 235000020636 oyster Nutrition 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 238000003933 environmental pollution control Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000010907 mechanical stirring Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 13
- 239000002086 nanomaterial Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000011257 shell material Substances 0.000 description 10
- 239000002114 nanocomposite Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 239000012496 blank sample Substances 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000276489 Merlangius merlangus Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000003516 soil conditioner Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000035568 catharsis Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Soil Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a nano iron/oyster shell composite material, and a preparation method and application thereof. The method comprises the following steps: activating the oyster shell by programmed heating and presintering; carrying out mechanical stirring and ultrasonic oscillation until iron ions or ferrous ions and the reducer are well dispersed in the porous structure of the oyster shell; and carrying out chemical reduction reaction to generate zero-valent nano iron on the pores and surface of the oyster shell in situ, thereby obtaining the nano iron oyster/shell composite material. By using the natural porous structure of the oyster shell as the carrier and the abundant minor elements in the oyster shell as the catalyst, the composite material fully displays the structure and component characteristics of the oyster shell, changes wastes into valuable substances, and well solves the problem of recovery of the oyster shell. Meanwhile, the composite material solves the problems of easy aggregation, easy oxidation, easy loss, difficulty in recovery and other application limitations of the nano iron in the field of environmental pollution control and restoration, can be widely used in purifying treatment of wastewater containing heavy metals (arsenic, cadmium and the like) and phosphorus as well as restoration of arsenic-polluted soil, and has favorable effects.
Description
Technical field
The present invention is specifically related to a kind of Nanoscale Iron/oyster shell composite and its preparation method and application, belongs to the preparation field of novel environmental Environmental capacity and repair materials.
Background technology
Along with the scale of oyster culture, how recycling accounts for the oyster shell of oyster quality 60% to reduce its environmental pollution, is realize a requisite ring in the sustainable development of oyster industry.Oyster shell has natural loose structure, and its main component is CaCO
3, simultaneously containing abundant trace element.In field of environment pollution control, utilize its loose structure more and be used as adsorbent.As patent 200910070793.3(mono-kind removes natural adsorbent of heavy metal ion in water and its preparation method and application) and 200910112699.X(sewage dephosphorization device of shuck filling biofilter), utilize the heavy metal in the suction-operated removal waste water of oyster shell and phosphorus respectively.Further studying application is mixed with other material by oyster shell, as removing pollutant material, fertilizer or soil conditioner.Lose the compound organic fertilizer manufacture method of function as patent 201310442158.X (a kind of oyster shell modified activated carbon sorbent and preparation method thereof), 201210573662.9(mono-kind have fertilizer conservation control), a 201310437007.5(soil conditioner and preparation method thereof) etc.Although these research application relate to the compound of oyster shell and other materials, complex method mostly is mixing or the load of machinery or physics, and the catharsis of composite fails to break through adsorption capacity to the restriction of material itself, makes it apply and is very restricted.
Nanoscale Iron has very strong reproducibility, can by the reduction degradation of contaminant of chemistry, realization be the chemical degradation of pollutant, can purify with the physical absorption of pollutant and form complementation.But, because nano material particle diameter is little, be in use easy to run off; Simultaneously by telluric magnetic force, electrostatic attraction and surface tension etc. affect between granule, Nanoscale Iron is easy to reunite and oxidized, thus causes the reduction of its reactivity and efficiency in the application.Therefore, by fabricated in situ, Nanoscale Iron is dispersed in duct and the surface of porous oyster shell material, forms meso-porous nano composite, not only can improve the dispersiveness of Nanoscale Iron, stability and utilization rate, thus break through the application restriction of above-mentioned Nanoscale Iron; Meanwhile, the restriction of oyster shell adsorption capacity can be broken through, the range of application of expansion oyster shell.
Relevant report nano material be combined with shell loaded article is less.The preparation method of patent 200810026526.1(shell powder supported active nano titanic oxide) and 200810026525.7(take oyster shell whiting as the nano titanic oxide impregnation preparation method of carrier) although etc. correlative study relate to the combination of shell material and nano material, but be all by methods such as dipping, spin coating, dipping or sprayings by nanomaterial loadings on oyster shell whiting carrier, nano material multi-load, at surface of shell, is difficult to enter into carrier inside duct preferably.At patent 201010281703.8(waste shell loaded with nano Cu
2o composite photocatalyst material and Synthesis and applications) research in, although related to the original position preparation of nano material, nano material has been obtained by being hydrolyzed, and growing amount is very unstable, also difficultly controls.As can be seen here, the compound research of nano material and shell material is scarcely out of swaddling-clothes, and correlative study does not relate to the compound of Nanoscale Iron and oyster shell; Meanwhile, in nano material and shell material complex method, do not relate to the in-situ chemical synthesis of nano-substance.Therefore, also just bibliographical information is had no by the chemical preparation Nanoscale Iron of original position and the research of oyster shell meso-porous nano composite.
The present invention is by carrying out the measure such as pretreatment and ultrasonic wave added stirring to oyster shell powder, iron ion or ferrous ion are distributed in advance equably in duct, oyster shell inside and outside portion, then borohydride salts reducing agent is introduced, by the chemical reaction of reducing agent and iron ion or ferrous ion, iron ion or ferrous ion in-situ reducing are become the Nanoscale Iron of zeroth order, thus achieve chemical reduction method original position and prepare Nanoscale Iron/oyster shell meso-porous nano composite.With dipping, spray and compare with hydrolysis, Nanoscale Iron/oyster shell meso-porous nano composite prepared by chemical reduction method original position has stronger anti acid alkali performance, the Nanoscale Iron distribution generated is stable and not easily run off and oxidized, can be widely used in purification and the reparation of the pollutants such as the organic matter in waste water, waste gas and soil, heavy metal.
Summary of the invention
The object of the present invention is to provide a kind of Nanoscale Iron/oyster shell meso-porous nano composite and its preparation method and application.The present invention prepares Nanoscale Iron/oyster shell meso-porous nano composite by chemical reduction method in duct, the inside and outside situ reduction of oyster shell, enhance the uniformity of Nanoscale Iron in composite, dispersiveness and non-oxidizability, solve nano material in conventional physical dipping and spraying load method and be difficult to enter inner, the easy loss in support materials duct and oxidized problem; Meanwhile, compared with the Hydrolyze method of nano material, because the Nanoscale Iron in composite is obtained by chemical reaction, thus the stability of composite and controllability are also increased greatly.
For achieving the above object, the present invention adopts following technical scheme:
A kind of Nanoscale Iron/oyster shell composite utilizes borohydride salts reducing agent, the iron ion be dispersed in advance in duct, oyster shell inside and outside portion or ferrous ion in-situ reducing become Nanoscale Iron and obtained composite.
The preparation method of Nanoscale Iron/oyster shell composite comprises the pretreatment of oyster shell, the fabricated in situ of composite and dry process, specifically comprises the following steps:
1) oyster shell pretreatment: oyster shell is clean with tap water, 100-600 DEG C of temperature programming pre-burning 1-2 h, constant temperature 1-2 h, it is for subsequent use in drier to grind to form 10-200 order oyster shell powder after naturally cooling; 100 DEG C, described temperature programming interval;
2) fabricated in situ of composite: the oyster shell powder of step 1) and source of iron solution are added in there-necked flask, ultrasonic wave added machinery stirring at low speed mixing 30-45 min(speed of agitator 500-1000 r/min, ultrasonic power 50-100 W, mixing temperature 15-20 DEG C), then borohydride salts solution is dripped under nitrogen protection, ultrasonic wave added machinery moderate-speed mixer reacts 15 min(speed of agitator 1000-2000 r/min, ultrasonic power 100-200 W, reaction temperature 15-50 DEG C); Described source of iron solution is FeSO
4, FeCl
2or FeCl
3in one, concentration is 0.05-0.45 mol/L; The quality of described oyster shell powder and the volume ratio of source of iron solution are 1 g:30 mL; Borohydride salts is KBH
4or NaBH
4in one, concentration is 0.5-0.9 mol/L, the volume ratio 1:10-1:6 of itself and source of iron solution.
3) dry process: by step 2) absolute ethyl alcohol rinse 5-7 time of gained solid phase reaction product, carry out vacuum drying under nitrogen protection, obtain Nanoscale Iron/oyster shell composite.
Described Nanoscale Iron/oyster shell composite is used for the purification of the pollutant such as organic matter, heavy metal and the reparation of As polluted soil in waste water, waste gas and soil.
Remarkable advantage of the present invention is:
(1) the present invention is by temperature programming pre-burning activation oyster shell, by increasing progressively step by step of mechanical agitation and sonic oscillation energy, iron ion or ferrous ion and reducing agent are distributed in the loose structure of oyster shell well, and complete Nanoscale Iron in oyster shell duct and the reaction of surperficial in-situ reducing, define New Type of Mesoporous nano composite material; This composite property is stablized, and has the performances such as absorption, catalysis and reaction, for containing the heavy metal such as arsenic, cadmium and the purification of phosphorus-containing wastewater and the repair process of As polluted soil, respond well;
(2) composite that obtains of the present invention is with the natural loose structure of oyster shell for carrier, with trace element abundant in oyster shell for catalyst, gives full play to oyster shell structure and ingredient properties, turns waste into wealth, solve the resource problem of oyster shell well; Meanwhile, the application limitations such as the easy reunion of Nanoscale Iron in environment pollution control and reparation field, oxidizable, easy loss and difficulty reclaim are solved by composite mesoporous; Possesses significant economic benefit.
Accompanying drawing explanation
Fig. 1 source of iron kind is on the impact of composite arsenic removal efficiency;
Fig. 2 oyster shell order number is on the impact of composite arsenic removal efficiency;
Fig. 3 reduction temperature is on the impact of composite arsenic removal efficiency;
Fig. 4 arsenic solution pH value is on the impact of composite arsenic removal efficiency;
When Fig. 5 composite is for removing the arsenic in solution, application of temperature is on the impact of composite arsenic removal efficiency;
Infrared spectrum (FTIR) figure of Fig. 6 composite;
Field emission scanning electron microscope (FESEM) figure of Fig. 7 composite.
Detailed description of the invention
The present invention's the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.
The arsenic solution that arsenic solution in the following example can adopt this area general can be NaAsO
2, As
2o
3solution, preferred As
2o
3solution.As
2o
3the preferred preparation method of solution is, gets 0.132 g As
2o
3be dissolved in alkaline solution, to be dissolved complete after be settled to 100 ml volumetric flasks, this solution is as arsenic stock solution.
Embodiment 1
The preparation method of Nanoscale Iron/oyster shell composite, concrete steps are:
1) oyster shell pretreatment: oyster shell is clean with tap water, 100-600 DEG C of temperature programming pre-burning 1h, constant temperature 1h, it is for subsequent use in drier to grind to form 65 order oyster shell powders after naturally cooling; 100 DEG C, described temperature programming interval;
2) fabricated in situ of composite: by oyster shell powder 1 g of step 1) and source of iron solution 30 mL(0.45 mol/L) add in there-necked flask; ultrasonic wave added machinery stirring at low speed mixes 30 min(speed of agitator 500 r/min; ultrasonic power 100 W; mixing temperature 20 DEG C), then drip KBH under nitrogen protection
4solution (0.9 mol/L) 5 mL, ultrasonic wave added machinery moderate-speed mixer reacts 15 min(speed of agitator 1000 r/min, ultrasonic power 100 W, reaction temperature 20 DEG C);
3) dry process: by step 2) gained solid phase reaction product with after absolute ethyl alcohol rinse 5 times, carry out vacuum drying under nitrogen protection, obtain Nanoscale Iron/oyster shell composite.
Select FeSO respectively according to the method described above
4, FeCl
2or FeCl
3for source of iron, prepare three kinds of composites.The composite equivalent obtained by different source of iron is added (pH:7 in arsenic stock solution, arsenic concentration: 2 mg/L), often kind of condition setting three groups of parallel and blank samples, after layer of air in nitrogen emptying, with put into after preservative film good seal constant temperature oscillation case react 24 h after (rotating speed: 200 r/min, temperature: 20 DEG C), get supernatant measure arsenic concentration, the composite relatively prepared by different source of iron to the removal effect of arsenic in solution, as shown in Figure 1.As can be seen from the figure, the composite that different sources of iron obtains all reaches more than 98%, with FeSO to the clearance of arsenic in solution
4the composite obtained for source of iron reaches more than 99% to the clearance of arsenic in solution, and effect is the most outstanding.
Embodiment 2
Respectively with NaBH
4and KBH
4for reducing agent, 65 order oyster shell powders, FeSO
4for source of iron, all the other parameters are identical with embodiment 1.The composite equivalent obtained by different reducing agent is added (pH:7 in arsenic stock solution, arsenic concentration: 2 mg/L), often kind of condition setting three groups of parallel and blank samples, after layer of air in nitrogen emptying, with put into after preservative film good seal constant temperature oscillation case react 24 h after (rotating speed: 200 r/min, temperature: 20 DEG C), get supernatant measure arsenic concentration, the composite relatively prepared with different reducing agent is to the removal effect of arsenic in solution, as shown in table 1.When with KBH
4during for reducing agent, can 99.80% be reached, Be very effective to the removal effect of arsenic in solution.
Table 1 reducing agent kind is on the impact of composite arsenic removal efficiency
Embodiment 3
Select 10,35,65,100,200 order oyster shell powders respectively, FeSO
4for source of iron, KBH
4for reducing agent, all the other parameters are identical with embodiment 1.The composite equivalent prepared by different meshes oyster shell powder is added (pH:7 in arsenic stock solution, arsenic concentration: 2 mg/L), often kind of condition setting three groups of parallel and blank samples, after layer of air in nitrogen emptying, with put into after preservative film good seal constant temperature oscillation case react 24 h after (rotating speed: 200 r/min, temperature: 20 DEG C), get supernatant measure arsenic concentration, relatively the composite prepared of different meshes oyster shell powder is to the removal effect of arsenic in solution, as shown in Figure 2.As can be seen from Figure 2, when oyster shell powder order number is lower than 100 order, obtained composite increases progressively the clearance of arsenic in solution always; When oyster shell powder order number is higher than 100 order, obtained composite reaches maximum to the clearance of arsenic in solution, remains unchanged.This is mainly because when oyster shell powder order number is lower, and oyster shell powder specific area is relatively little, and Nanoscale Iron does not fully contact with oyster shell powder, and therefore obtained composite goes arsenic rate lower; Along with oyster shell powder order number increases, oyster shell powder particle is more and more thinner, and specific area increases, and Nanoscale Iron is dispersed in inside and the surface of oyster shell powder fully, and obtained material property is given prominence to, and goes arsenic rate high.
Embodiment 4
Select 20 DEG C, 25 DEG C, 30 DEG C, 40 DEG C and 50 DEG C of water-baths respectively, 65 order oyster shell powders, FeSO
4for source of iron, KBH
4for reducing agent, all the other parameters are identical with embodiment 1, prepare composite.The composite equivalent prepared under different temperatures is added (pH:7 in arsenic stock solution, arsenic concentration: 2 mg/L), often kind of condition setting three groups of parallel and blank samples, after layer of air in nitrogen emptying, with put into after preservative film good seal constant temperature oscillation case react 24 h after (rotating speed: 200 r/min, temperature: 20 DEG C), get supernatant and measure arsenic concentration, composite under more different preparation temperature is to the removal effect of arsenic in solution, as shown in Figure 3 (NI is nano-iron material, and NI/OS is Nanoscale Iron/oyster shell composite).Known from Fig. 3, no matter be nano-iron material, or Nanoscale Iron/oyster shell composite that the present invention obtains, along with the rising of reduction reaction temperature, arsenic removal rate is on a declining curve generally; But the compound of Nanoscale Iron and oyster shell, the downward trend of composite after higher than 30 DEG C in temperature range is curbed, under the same terms, the arsenic removal rate of composite is higher than simple Nanoscale Iron, and illustrate that composite is less by the impact of preparation temperature, performance is more stable.
Embodiment 5
Select 65 order oyster shell powders, FeSO
4for source of iron, KBH
4for reducing agent, in 20 DEG C of water-baths, all the other parameters are identical with embodiment 1, prepare composite.Obtained composite equivalent is added in the arsenic stock solution of pH difference 3,5,7,9 and 11 (arsenic concentration: 2 mg/L), often kind of condition setting three groups of parallel and blank samples, after layer of air in nitrogen emptying, with put into after preservative film good seal constant temperature oscillation case react 24 h after (rotating speed: 200 r/min, temperature: 20 DEG C), get supernatant and measure arsenic concentration, compare the removal effect of composite to different pH value arsenic containing solution, as shown in Figure 4.Nano-iron material is comparatively large by the impact of extraneous pH value, and the Nanoscale Iron that the present invention obtains/oyster shell composite does not affect by extraneous pH value, illustrates that, by after Nanoscale Iron and oyster shell compound, stable performance, does not affect by outside environmental elements during application.
Embodiment 6
Select 65 order oyster shell powders, FeSO
4for source of iron, KBH
4for reducing agent, in 20 DEG C of water-baths, all the other parameters are identical with embodiment 1, prepare composite.Obtained composite equivalent is added (pH:7 in arsenic stock solution, arsenic concentration: 2 mg/L), often kind of condition setting three groups of parallel and blank samples, after layer of air in nitrogen emptying, after reacting 24 h with the constant temperature oscillation case putting into temperature setting after preservative film good seal and be respectively 0 DEG C, 10 DEG C, 20 DEG C, 40 DEG C and 50 DEG C (rotating speed: 200 r/min), get supernatant and measure arsenic concentration, compare the removal effect of composite to the arsenic containing solution of different temperatures, as shown in Figure 5.Result shows, the removal effect of composite to the arsenic containing solution of different temperatures is substantially the same, illustrates that the composite property that the present invention obtains is stablized, does not affect during application by ambient temperature factor.
Embodiment 7
U.S. Therm Electron company Nicolex 380 type Fourier infrared spectrograph is adopted to analyze the Nanoscale Iron in the present invention/oyster shell composite (NI/OS), simple Nanoscale Iron (NI) and oyster shell powder (OS) three kinds of samples.As shown in Figure 6, compared with simple oyster shell material, Nanoscale Iron/oyster shell composite is at 712.35 cm
-1, 878.87 cm
-1with 1417.83 cm
-1the CaCO at place
3peak value weakens, and illustrates that Nanoscale Iron load is at oyster shell material surfaces externally and internally; Compared with simple nano-iron material, Nanoscale Iron/oyster shell composite is at 616.84 cm
-1the Fe-O stretching vibration peak value at place weakens, and illustrate that the non-oxidizability of Nanoscale Iron/oyster shell composite strengthens, in composite, between Nanoscale Iron and oyster shell, existing physical bond also has chemical bonding effect.
Embodiment 8
Company of NEC JSM-5310LV is adopted to carry out field emission scanning electron microscope (FESEM) and elementary analysis (EDX), as table 2 and Fig. 7 to the Nanoscale Iron in the present invention/oyster shell composite (NI/OS), simple Nanoscale Iron and oyster shell powder (OS) three kinds of samples.As known from Table 2, in composite, Fe element is increased to 50.23%(Wt% from not detecting oyster shell), show that ferro element accounts for significant proportion at composite, Nanoscale Iron has been got involved in oyster shell well; Fig. 7 shows, and easily reunite different from simple Nanoscale Iron, in Nanoscale Iron/oyster shell composite, Nanoscale Iron is dispersed in the channel surfaces of oyster shell well, and agglomeration obviously weakens.
Table 2 Nanoscale Iron/oyster shell composite and oyster shell powder elementary analysis (EDX)
A system is without detecting.
Nanoscale Iron prepared by the present invention/oyster shell composite can be used for, purification of waste water field, as: process pink, green, the resistance to dyeing waste water such as tanned, sky blue, process phosphorous organic wastewater of Denging, process is containing heavy metal wastewater therebies such as arsenic, chromium and cadmiums, only need get a certain amount of composite drops in water, becomes clarification, filter to liquid; Waste gas purification field, as: be used as factory's organic waste-gas purification agent and the deodorant such as refrigerator and shoes, only need get a certain amount of Nanoscale Iron/oyster shell composite non-woven fabrics and package, be placed in exhaust steam passage; Contaminated soil remediation field, as the reparation of the heavy-metal contaminated soils such as arsenic, chromium and cadmium, only need get a certain amount of composite with contaminated soil mixes, and just can reach the heavy metals such as arsenic, chromium and the cadmium in passivation soil, reduce its biological effectiveness, improve the object of acid ground soil property simultaneously.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. Nanoscale Iron/oyster shell composite, it is characterized in that: described Nanoscale Iron/oyster shell composite take borohydride salts as reducing agent, the iron ion be dispersed in advance in duct, oyster shell inside and outside portion or ferrous ion in-situ reducing are become Nanoscale Iron and obtain.
2. prepare a method for Nanoscale Iron as claimed in claim 1/oyster shell composite, it is characterized in that: specifically comprise the following steps:
1) oyster shell pretreatment: oyster shell is clean with tap water, 100-600 DEG C of temperature programming pre-burning 1-2 h, constant temperature 1-2 h, it is for subsequent use in drier to grind to form 10-200 order oyster shell powder after naturally cooling;
2) fabricated in situ of composite: the oyster shell powder of step 1) and source of iron solution are added in there-necked flask, ultrasonic wave added machinery stirring at low speed 30-45 min, drip borohydride salts reducing agent under nitrogen protection, ultrasonic wave added machinery moderate-speed mixer reacts 15 min;
3) dry process: by step 2) solid product absolute ethyl alcohol rinse 5-7 time of gained, vacuum drying under nitrogen protection, obtains and to obtain Nanoscale Iron/oyster shell composite.
3. the preparation method of Nanoscale Iron according to claim 2/oyster shell composite, is characterized in that: the oyster shell powder described in step 1) is obtained by the temperature programming pre-burning of 100 DEG C, interval.
4. the preparation method of Nanoscale Iron according to claim 2/oyster shell composite, is characterized in that: step 2) described in source of iron solution be FeSO
4, FeCl
2or FeCl
3one in solution, concentration is 0.05-0.45 mol/L; The quality of described oyster shell powder and the volume ratio of source of iron solution are 1 g:30 mL; Described borohydride salts reducing agent is KBH
4or NaBH
4, concentration is 0.5-0.9 mol/L, and it is greater than 1:10 with source of iron liquor capacity ratio.
5. the preparation method of Nanoscale Iron according to claim 2/oyster shell composite, is characterized in that: step 2) in the rotating speed 500-1000 r/min of low rate mixing, ultrasonic power 100-200 W, temperature 15-20 DEG C; The rotating speed 1000-2000 r/min of moderate-speed mixer, ultrasonic power 50-100 W, reduction reaction temperature 15-50 DEG C.
6. an application for Nanoscale Iron as claimed in claim 1/oyster shell composite, is characterized in that: described Nanoscale Iron/oyster shell composite is used for the purification removal of Phosphorus From Wastewater, arsenic and cadmium and the reparation of As polluted soil.
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