CN103480323B - A kind of method of one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process - Google Patents
A kind of method of one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process Download PDFInfo
- Publication number
- CN103480323B CN103480323B CN201310396313.9A CN201310396313A CN103480323B CN 103480323 B CN103480323 B CN 103480323B CN 201310396313 A CN201310396313 A CN 201310396313A CN 103480323 B CN103480323 B CN 103480323B
- Authority
- CN
- China
- Prior art keywords
- microballoon
- tri
- hierarchy
- iron tetroxide
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 13
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 229910001385 heavy metal Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 206010013786 Dry skin Diseases 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 7
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 239000002086 nanomaterial Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- AYRVGWHSXIMRAB-UHFFFAOYSA-M sodium acetate trihydrate Chemical class O.O.O.[Na+].CC([O-])=O AYRVGWHSXIMRAB-UHFFFAOYSA-M 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 229940032296 ferric chloride Drugs 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003541 multi-stage reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of method that the present invention relates to one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process, at room temperature, ferric salt, sodium acetate trihydrate are dissolved in a certain amount of ethylene glycol, 10 milliliters of lauryl mercaptans will be added again in mixed solution, and stir as suspension, heat 8 hours at 180 DEG C again, cool, wash.The present invention compared with prior art, lauryl mercaptan can be attached to the surface of tri-iron tetroxide effectively, ferriferrous oxide nano-particle is stoped to be grown up further, can promote ferriferrous oxide nano-particle reunion each other, thus self assembly generates the tri-iron tetroxide microballoon with hierarchy simultaneously.Adopt one-step liquid-phase reaction, simple to operate, raw material is cheap, be easy to manipulation.Product to the selective absorption Be very effective of lead ion in the aqueous solution, and can recycle.
Description
Technical field
A kind of method that the present invention relates to one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process, be specifically related to a kind of can the synthetic method of hierarchy tri-iron tetroxide microballoon of selective absorption lead ion.
Background technology
In recent years, the micro Nano material with hierarchy has excellent character and application prospect and receiving much concern widely because of it.The micro Nano material size of hierarchy is comparatively large, but is formed by the nano material unit self assembly that size is less, has high specific area.This kind of material has function and the advantageous property of nanometer and micrometer structure simultaneously, by the form of hierarchy, has played the respective advantage of micron, nano material to greatest extent and has suppressed it not enough.
The method of the synthesis hierarchy micro Nano material reported at present has template, multistep reaction method, vapour deposition process and liquid phase method etc.Template finally needs template to be removed by methods such as calcining, chemical attacks, and the operation of removing template may have an impact to final product.Multistep reaction method, owing to relating to the reaction of multiple step, operates comparatively loaded down with trivial details, is not easy to control.One-step liquid-phase reaction has simple to operate, is easy to control, and requiring the advantages such as low to reaction unit, is the Perfected process preparing hierarchy micro Nano material.
Tri-iron tetroxide micro Nano material has unique ferromagnetism, thus receives and pays close attention to widely, all have wide practical use in magnetic recording, magnetic fluid, magnetic resonance imaging and target medicine carrier etc.In recent years, the report of existing a large amount of synthesis about tri-iron tetroxide micro Nano material, comprises nanometer rods, nano wire, microballoon etc.In addition, the research about ferriferrous oxide nano composite is also a lot.
Effluent containing heavy metal ions pollutes has become a global problem.Heavy metal ion is hypertoxic, and has been found that and in a lot of, had influence on the health of people, even if still have impact when its concentration is very low.In heavy-metal pollution, the pollution of lead ion is modal.Lead ion can hinder the biosynthesis of heme, suppresses several synthesis containing Zn-ef ficiency enzyme, with nucleic acid and t-RNA effect and then the synthesis affecting protein, and can assemble in bone.
The method of traditional removing heavy metal ions in wastewater has: chemical precipitation method, coagulation-flocculence, ion-exchange, membrane filter method, electroosmose process and absorption method etc.The features such as in these techniques, the cost that absorption method has because of it is low, and the high and secondary pollution of efficiency is less, are considered to technology the most easily.Adsorbent mainly active carbon conventional at present, porous silica etc.These adsorbents can adsorb poisonous heavy metal ion at short notice, and have higher adsorption efficiency.But but have the following disadvantages: poisonous heavy metal ion is present in a large amount of waste water, after the complete heavy metal ion of adsorbent, usually adopt the methods such as sedimentation, filtration and centrifugation to be separated from water by adsorbent, but the speed of these method process is slow, wastes time and energy.
Recently, magnetic composite obtains in field of waste water treatment and pays close attention to widely.Magnetic composite gathers around magnetic component, has good external magnetic field response characteristic, to be easy to attract by external magnetic field.The effect magnetic composite of outside magnetic field can be collected and is separated easily, and other functional components in magnetic composite can provide the adsorption function of heavy metal ion, such as: the Fe with nucleocapsid structure
3o
4siO
2and Fe
3o
4siO in shitosan magnetic composite
2have superior heavy metal ion adsorbed ability with shitosan, therefore these magnetic composites can be used as the heavy metal ion in adsorbent removing waste water.In these magnetic composites, Fe
3o
4only play the effect of a response external magnetic field, then what effect is not played to removing heavy metal ion.
The shortcoming of prior art: the 1. synthesis of hierarchy adopts multistep reaction or template synthesis, and step is more complicated.2. nonmagnetic adsorbent is deposited and be there is separation difficulty, the shortcoming such as time-consuming in use.
Summary of the invention
The object of the present invention is to provide a kind of method of one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process, the one-step liquid-phase reaction of employing, simple to operate, raw material is cheap, be easy to manipulation.Product to the selective absorption Be very effective of lead ion in the aqueous solution, and can recycle.
Concrete technical scheme is as follows:
The method of one-step synthesis hierarchy tri-iron tetroxide microballoon, adopts following steps: ferric salt, sodium acetate trihydrate are dissolved in a certain amount of ethylene glycol, then add lauryl mercaptan in mixed solution, and stirs as emulsion, heats, cooling and washing.
Further, specifically comprise the steps:
(1) ferric salt, sodium acetate trihydrate are dissolved in a certain amount of ethylene glycol;
(2) be stirred to dissolving and obtain mixed solution;
(3) in mixed solution obtained above, add a certain amount of lauryl mercaptan, fully stir into emulsion;
(4) solution is loaded container;
(5) heat;
(6) cool;
(7) product is collected;
(8) wash;
(9) dry.
Described in step (1), ferric salt is ferric chloride hexahydrate, and/or Fe(NO3)39H2O.
Step (1) and (2) are at room temperature carried out.
The mixed liquor of gained is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag in step (4).
Heat 8 ~ 48 hours at 180 ~ 200 DEG C in step (5).
Step naturally cools to room temperature in (6).
Step collects product with externally-applied magnetic field in (7).
Step (8) middle acetone and absolute ethanol washing are for several times.
60 DEG C of dryings about 2 hours in vacuum drying chamber in step (9).
The application process of the product of the method for above-mentioned one-step synthesis hierarchy tri-iron tetroxide microballoon, is applied to the heavy metal ion in adsorption aqueous solution, comprises the steps:
Under a, room temperature, by 0.2g hierarchy Fe
3o
4microballoon joins the Pb that 50mL concentration is 10mg/L
2+(or Cd
2+, Cu
2+) ion the aqueous solution in and with mechanical stirring device stir, make Fe
3o
4microballoon and Pb
2+ion fully contacts, and then gets 3mL solution every 10 minutes, removes Fe with externally-applied magnetic field
3o
4, more remaining Pb in analytical solution
2+the concentration of ion.
B, to hierarchy Fe
3o
4microballoon recycle research as follows: get 0.2gFe
3o
4be distributed to the Pb that 50mL concentration is 10mg/L
2+also constantly stir in solution, after the absorption of 40 minutes, under the effect of externally-applied magnetic field, by Fe
3o
4microballoon is collected completely, by weak acid solution desorption under ultrasonic effect of 100mL, then use distilled water washes clean, adsorbent again joins in identical solution and carries out next one circulation, repeat aforesaid operations and recycle 5 times altogether, to Pb remaining in solution after each absorption
2+concentration detects.
The present invention is compared with the technology of existing Liquid preparation methods tri-iron tetroxide micro Nano material, lauryl mercaptan can be attached to the surface of tri-iron tetroxide effectively, ferriferrous oxide nano-particle is stoped to be grown up further, can promote ferriferrous oxide nano-particle reunion each other, thus self assembly generates the tri-iron tetroxide microballoon with hierarchy simultaneously.This synthetic method one step can obtain target product, simple to operate, raw material is cheap, be easy to manipulation.
Accompanying drawing explanation
Fig. 1 is hierarchy Fe prepared by embodiment 1
3o
4the X-ray diffraction pattern of microballoon.
Fig. 2 is hierarchy Fe prepared by embodiment 1
3o
4the stereoscan photograph of microballoon.
Fig. 3 is hierarchy Fe prepared by embodiment 1
3o
4the transmission electron microscope photo of microballoon.
Fig. 4 is hierarchy Fe prepared by embodiment 2
3o
4the stereoscan photograph of microballoon.
Fig. 5 is hierarchy Fe prepared by embodiment 3
3o
4the stereoscan photograph of microballoon.
Fig. 6 is hierarchy Fe prepared by embodiment 4
3o
4the stereoscan photograph of microballoon.
Fig. 7 is hierarchy Fe prepared by embodiment 5
3o
4the stereoscan photograph of microballoon.
Fig. 8 is hierarchy Fe prepared by embodiment 6
3o
4the stereoscan photograph of microballoon.
Fig. 9 is hierarchy Fe prepared by embodiment 7
3o
4the stereoscan photograph of microballoon.
Figure 10 is the hierarchy Fe using embodiment 1 to prepare
3o
4the kinetic curve of lead, cadmium and copper ion in microballoon adsorption aqueous solution.
Figure 11 is the hierarchy Fe recycling embodiment 1 preparation
3o
4in microballoon adsorption aqueous solution, lead ion removes efficiency change figure.
Detailed description of the invention
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
The method of one-step synthesis hierarchy tri-iron tetroxide microballoon, a, at room temperature, ferric salt, sodium acetate trihydrate are dissolved in a certain amount of ethylene glycol, under room temperature, be stirred to dissolving and obtain mixed solution, in mixed solution obtained above, add a certain amount of lauryl mercaptan, fully stir into emulsion; B, the mixed liquor of gained in step a is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag, heat 8 ~ 48 hours at 180 ~ 200 DEG C, naturally cool to room temperature subsequently.Collect product with externally-applied magnetic field, with acetone and absolute ethanol washing for several times, finally 60 DEG C of dryings about 2 hours in vacuum drying chamber, described ferric salt is ferric chloride hexahydrate, Fe(NO3)39H2O.In this reaction, ferric salt is as source of iron, and sodium acetate is as alkali source, and ethylene glycol to be held concurrently reducing agent as solvent, and lauryl mercaptan is as emulsifying agent and surfactant, and end reaction generates the tri-iron tetroxide microballoon of hierarchy.Lauryl mercaptan is attached on the surface of product, utilizes the organic solvent such as acetone and ethanol to be washed away by the lauryl mercaptan molecule of its surface, reduces organic molecule to the impact caused during Characterization of The Products.
Embodiment 1:
A, at room temperature, 1.34 grams of ferric chloride hexahydrates and 3.4 grams of sodium acetate trihydrates are dissolved in the ethylene glycol of 30 milliliters, under room temperature, are stirred to dissolving completely and obtain mixed solution, in mixed solution obtained above, add the lauryl mercaptan of 10 milliliters, fully stir into emulsion;
B, the emulsion of gained in step a is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag, heat 8 hours at 180 DEG C, naturally cool to room temperature subsequently.Collect product with externally-applied magnetic field, use acetone and absolute ethanol washing for several times respectively, finally 60 DEG C of dryings about 2 hours in vacuum drying chamber, with to be characterized.
Its result is as shown in accompanying drawing 1 ~ 3: the Fe of what X-ray diffraction pattern explanation the method for Fig. 1 obtained is pure orthorhombic phase
3o
4.The scanning electron microscope (SEM) photograph of Fig. 2 shows that this product is by the microballoon of the hierarchy of a large amount of self-assembly.The favorable dispersibility of these microballoons, particle diameter is more homogeneous, average grain diameter about 400 nanometer.The particle diameter of the nano particle of composition microballoon is 10 ~ 20 nanometers.Fig. 3 is the transmission electron microscope picture of product, shows that these microballoons are by less self-assembly equally, and is solid structure.
Embodiment 2:
A, at room temperature, 1.34 grams of ferric chloride hexahydrates and 3.4 grams of sodium acetate trihydrates are dissolved in the ethylene glycol of 35 milliliters, under room temperature, are stirred to dissolving completely and obtain mixed solution, in mixed solution obtained above, add the lauryl mercaptan of 5 milliliters, fully stir into emulsion;
B, the mixed liquor of gained in step a is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag, heat 8 hours at 180 DEG C, naturally cool to room temperature subsequently.Collect product with externally-applied magnetic field, use acetone and absolute ethanol washing for several times respectively, finally 60 DEG C of dryings about 2 hours in vacuum drying chamber, with to be characterized.
Its result is as shown in Figure 4.
The scanning electron microscopic picture of Fig. 4 shows the microballoon obtaining tri-iron tetroxide, but the uniformity of these microballoons is poor, and wherein some is assembled by granule, and some is then only formed by several particle assembling, and some also presents the characteristic of monocrystalline even.Illustrate if the consumption of lauryl mercaptan is very few, can not effectively stop growing up of ferriferrous oxide particles, be thus difficult to the tri-iron tetroxide microballoon obtaining hierarchy.
Embodiment 3:
A, at room temperature, 1.34 grams of ferric chloride hexahydrates and 3.4 grams of sodium acetate trihydrates are dissolved in the ethylene glycol of 20 milliliters, under room temperature, are stirred to dissolving completely and obtain mixed solution, in mixed solution obtained above, add the lauryl mercaptan of 20 milliliters, fully stir into emulsion;
B, the mixed liquor of gained in step a is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag, heat 8 hours at 180 DEG C, naturally cool to room temperature subsequently.Collect product with externally-applied magnetic field, use acetone and absolute ethanol washing for several times respectively, finally 60 DEG C of dryings about 2 hours in vacuum drying chamber, with to be characterized.
Its result as shown in Figure 5.
The scanning electron microscopic picture of Fig. 5 shows that obtained product is the tri-iron tetroxide microballoon with hierarchy, and result is similar to example 2, but the particle diameter of the nano particle of composition microballoon slightly reduces.Illustrate that the consumption increasing lauryl mercaptan can suppress the growth of ferriferrous oxide nano-particle further.
Embodiment 4:
A, at room temperature, 1.34 grams of ferric chloride hexahydrates and 3.4 grams of sodium acetate trihydrates are dissolved in the ethylene glycol of 30 milliliters, under room temperature, are stirred to dissolving completely and obtain mixed solution, in mixed solution obtained above, add the lauryl mercaptan of 10 milliliters, fully stir into emulsion;
B, the mixed liquor of gained in step a is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag, heat 19 hours at 180 DEG C, naturally cool to room temperature subsequently.Collect product with externally-applied magnetic field, use acetone and absolute ethanol washing for several times respectively, finally 60 DEG C of dryings about 2 hours in vacuum drying chamber, with to be characterized.
Its result as shown in Figure 6.
The scanning electron microscopic picture of Fig. 6 shows that the microballoon pattern of this hierarchy is similar to the product morphology of example 2,3, but wherein there is a small amount of larger nano particle, prolongation along with the reaction time is described, ferriferrous oxide nano-particle has the trend of growing up gradually.
Embodiment 5:
A, at room temperature, 1.34 grams of ferric chloride hexahydrates and 3.4 grams of sodium acetate trihydrates are dissolved in the ethylene glycol of 30 milliliters, under room temperature, are stirred to dissolving completely and obtain mixed solution, in mixed solution obtained above, add the lauryl mercaptan of 10 milliliters, fully stir into emulsion;
B, the mixed liquor of gained in step a is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag, heat 48 hours at 180 DEG C, naturally cool to room temperature subsequently.Collect product with externally-applied magnetic field, use acetone and absolute ethanol washing for several times respectively, finally 60 DEG C of dryings about 2 hours in vacuum drying chamber, with to be characterized.
Its result as shown in Figure 7.
The scanning electron microscopic picture of Fig. 7 shows that the microballoon pattern of this hierarchy is similar to the product morphology of example 5, the shared ratio of wherein larger nano particle is larger, further illustrate the prolongation along with the reaction time, ferriferrous oxide nano-particle has the trend of growing up gradually.
Embodiment 6:
A, at room temperature, 1.34 grams of ferric chloride hexahydrates and 3.4 grams of sodium acetate trihydrates are dissolved in the ethylene glycol of 30 milliliters, under room temperature, are stirred to dissolving completely and obtain mixed solution, in mixed solution obtained above, add the lauryl mercaptan of 10 milliliters, fully stir into emulsion;
B, the mixed liquor of gained in step a is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag, heat 8 hours at 200 DEG C, naturally cool to room temperature subsequently.Collect product with externally-applied magnetic field, use acetone and absolute ethanol washing for several times respectively, finally 60 DEG C of dryings about 2 hours in vacuum drying chamber, with to be characterized.
Its result as shown in Figure 8.
The scanning electron microscopic picture of Fig. 8 shows that obtained product is the tri-iron tetroxide microballoon with hierarchy, and result is similar to example 2, but the particle diameter of the nano particle of composition microballoon slightly increases.Rising along with reaction temperature is described, ferriferrous oxide nano-particle can be grown up.
Embodiment 7:
A, at room temperature, 2.02 grams of Fe(NO3)39H2Os and 3.4 grams of sodium acetate trihydrates are dissolved in the ethylene glycol of 30 milliliters, under room temperature, are stirred to dissolving completely and obtain mixed solution, in mixed solution obtained above, add the lauryl mercaptan of 10 milliliters, fully stir into emulsion;
B, the mixed liquor of gained in step a is loaded in the autoclave of inner liner polytetrafluoroethylene inner bag, heat 8 hours at 180 DEG C, naturally cool to room temperature subsequently.Collect product with externally-applied magnetic field, use acetone and absolute ethanol washing for several times respectively, finally 60 DEG C of dryings about 2 hours in vacuum drying chamber, with to be characterized.
Its result as shown in Figure 9.
Although the scanning electron microscopic picture of Fig. 9 shows that the product obtained is the tri-iron tetroxide microballoon with hierarchy, particle size is uneven, and the size forming the ferriferrous oxide nano-particle of microballoon is also very uneven.
The embodiment of the heavy metal ion in adsorption aqueous solution:
Under a, room temperature, by the hierarchy Fe synthesized by 0.2g example 1
3o
4microballoon joins the Pb that 50mL concentration is 10mg/L
2+(or Cd
2+, Cu
2+) ion the aqueous solution in and with mechanical stirring device stir, make Fe
3o
4microballoon and Pb
2+ion fully contacts, and then gets 3mL solution every 10 minutes, removes Fe with externally-applied magnetic field
3o
4, more remaining Pb in analytical solution
2+the concentration of ion.
B, to hierarchy Fe
3o
4microballoon recycle research as follows: get 0.2gFe
3o
4be distributed to the Pb that 50mL concentration is 10mg/L
2+also constantly stir in solution, after the absorption of 40 minutes, under the effect of externally-applied magnetic field, by Fe
3o
4microballoon is collected completely, and by weak acid solution desorption under ultrasonic effect of 100mL, then use distilled water washes clean, adsorbent again joins in identical solution and carries out next one circulation, repeats aforesaid operations and recycles 5 times altogether.To Pb remaining in solution after each absorption
2+concentration detects.
Test result as Fig. 9, shown in 10:
Figure 9 shows that the hierarchy Fe prepared by example 1
3o
4microballoon removes the Pb in the aqueous solution respectively
2+, Cu
2+and Cd
2+etc. the removal efficiency figure of heavy metal ion.Wherein C
0pb
2+initial concentration (C
0=10mgL
– 1), C is the concentration after absorption.
The initial concentration of these heavy metal ion is 10mgL
– 1.Pb can be found out
2+concentration just promptly reduced within initial 10 minutes, and Cu
2+and Cd
2+there is no great change, subsequently Pb
2+concentration with also have reduce but reduce speed obviously slow down, after 30 minutes, Pb
2+concentration almost no longer changes, and shows that this adsorbent has now reached saturated, by calculating known hierarchy Fe
3o
4microballoon is to Pb
2+removal rate can reach 97%.Above experimental result shows the Fe of hierarchy
3o
4microballoon can optionally by Pb
2+from rare aqueous solution, absorption is fallen effectively.
As can be seen from Figure 10 Fe in process is being recycled
3o
4the adsorption efficiency of adsorbent does not significantly change, and this has absolutely proved the Fe of hierarchy
3o
4microballoon has excellent desorption ability and recycles ability.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.
Claims (8)
1. the method for one-step synthesis hierarchy tri-iron tetroxide microballoon, is characterized in that, comprise the steps:
(1) ferric chloride hexahydrate and/or Fe(NO3)39H2O, sodium acetate trihydrate are dissolved in a certain amount of ethylene glycol;
(2) be stirred to dissolving and obtain mixed solution;
(3) in mixed solution obtained above, add lauryl mercaptan, fully stir into emulsion;
(4) solution is loaded container;
(5) heat;
(6) cool;
(7) product is collected;
(8) wash;
(9) dry;
Heat 8 ~ 48 hours at 180 ~ 200 DEG C in step (5);
Described hierarchy tri-iron tetroxide microballoon is applied to the heavy metal ion in adsorption aqueous solution.
2. the method for one-step synthesis hierarchy tri-iron tetroxide microballoon as claimed in claim 1, it is characterized in that, step (1) and (2) are at room temperature carried out.
3. the method for one-step synthesis hierarchy tri-iron tetroxide microballoon as claimed in claim 2, is characterized in that, is loaded by the mixed liquor of gained in the autoclave of inner liner polytetrafluoroethylene inner bag in step (4).
4. the method for one-step synthesis hierarchy tri-iron tetroxide microballoon as claimed in claim 1, it is characterized in that, step naturally cools to room temperature in (6).
5. the method for one-step synthesis hierarchy tri-iron tetroxide microballoon as claimed in claim 4, it is characterized in that, step collects product with externally-applied magnetic field in (7).
6. the method for one-step synthesis hierarchy tri-iron tetroxide microballoon as claimed in claim 5, is characterized in that, step (8) middle acetone and absolute ethanol washing are for several times.
7. the method for one-step synthesis hierarchy tri-iron tetroxide microballoon as claimed in claim 6, is characterized in that, 60 DEG C of dryings about 2 hours in vacuum drying chamber in step (9).
8. the application process of product prepared by the method for one-step synthesis hierarchy tri-iron tetroxide microballoon according to any one of claim 1-7, is characterized in that, be applied to the heavy metal ion in adsorption aqueous solution, comprise the steps:
Under a, room temperature, by 0.2g hierarchy Fe
3o
4microballoon joins the Pb that 50mL concentration is 10mg/L
2+in the aqueous solution of ion and with mechanical stirring device stir, make Fe
3o
4microballoon and Pb
2+ion fully contacts, and then gets 3mL solution every 10 minutes, removes Fe with externally-applied magnetic field
3o
4, more remaining Pb in analytical solution
2+the concentration of ion;
B, to hierarchy Fe
3o
4microballoon recycle research as follows: get 0.2gFe
3o
4be distributed to the Pb that 50mL concentration is 10mg/L
2+also constantly stir in solution, after the absorption of 40 minutes, under the effect of externally-applied magnetic field, by Fe
3o
4microballoon is collected completely,
By weak acid solution desorption under ultrasonic effect of 100mL, then use distilled water washes clean, adsorbent joins phase again
Carry out next one circulation in same solution, repeat aforesaid operations and recycle 5 times altogether, remain in solution after each absorption
Pb
2+concentration detects;
Described heavy metal ion can also be Cd
2+or Cu
2+.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310396313.9A CN103480323B (en) | 2013-09-03 | 2013-09-03 | A kind of method of one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310396313.9A CN103480323B (en) | 2013-09-03 | 2013-09-03 | A kind of method of one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103480323A CN103480323A (en) | 2014-01-01 |
| CN103480323B true CN103480323B (en) | 2016-04-27 |
Family
ID=49821109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310396313.9A Expired - Fee Related CN103480323B (en) | 2013-09-03 | 2013-09-03 | A kind of method of one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103480323B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596501A (en) * | 2016-11-23 | 2017-04-26 | 深圳先进技术研究院 | Magnetic movable Raman enhanced chip, and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883934A (en) * | 2016-04-18 | 2016-08-24 | 吉林师范大学 | Method for preparing water-soluble superparamagnetic Fe3O4 hollow spheres |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263886A (en) * | 2013-06-06 | 2013-08-28 | 湖北大学 | Hydrothermal preparation method and application of magnetic ferroferric oxide nanochain |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130105397A1 (en) * | 2010-01-12 | 2013-05-02 | Council Of Scientific & Industrial Research | Magnetic dye-adsorbent catalyst |
-
2013
- 2013-09-03 CN CN201310396313.9A patent/CN103480323B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263886A (en) * | 2013-06-06 | 2013-08-28 | 湖北大学 | Hydrothermal preparation method and application of magnetic ferroferric oxide nanochain |
Non-Patent Citations (3)
| Title |
|---|
| 单分散Fe3O4亚微米球的合成与表征;路苹 等;《无机化学学报》;20100731;第26卷(第7期);第1177-1182页 * |
| 可循环利用的重金属离子吸附剂的制备与性能研究;余响林 等;《长江大学学报（自然科学版）》;20110430;第8卷(第4期);第14-17页 * |
| 巯基修饰和胡敏酸包裹纳米 Fe3O4颗粒的制备及其对溶液中Pb2+Cd2+Cu2+的吸附效果研究;王萌 等;《农业环境科学学报》;20110831;第30卷(第8期);第1669-1674页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596501A (en) * | 2016-11-23 | 2017-04-26 | 深圳先进技术研究院 | Magnetic movable Raman enhanced chip, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103480323A (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582880B (en) | A kind of molybdenum disulfide/MIL-101 composite photocatalyst material and the preparation method and application thereof | |
| CN107096494A (en) | A kind of preparation and application method of magnetic core-shell nano-compound adsorbent | |
| CN106732358B (en) | A kind of biomass carbonization microballoon loading iron oxide and its preparation and application | |
| CN110102267A (en) | A kind of aluminium base MOFs/ chitosan compound microsphere and its preparation method and application | |
| CN107961764A (en) | A kind of preparation method of carboxymethyl-beta-cyclodextrin functional magnetic mesoporous silicon microballoon | |
| CN105032375B (en) | Preparation method of magnetic graphite-based heavy metal adsorbing material | |
| CN107824157B (en) | Magnetic gamma-Fe prepared by using ferro-manganese mud2O3Method for removing arsenic in water by using adsorbing material | |
| CN104117339B (en) | For preparation method and the application process thereof of the adsorbent of absorbing dye | |
| CN102716730A (en) | Preparation method for novel nano magnetic cyclodextrin/graphene biological adsorption material | |
| CN103466702A (en) | Method for preparing porous bismuth oxide nano-material without template | |
| JP2008030975A (en) | Substance-adsorptive magnetite and its manufacturing method | |
| CN105536688B (en) | A kind of magnetic core nanoparticle of Kocide SD cladding and its preparation and application | |
| CN109876779A (en) | A kind of mesoporous nano Fe3O4The preparation and application of chitosan core-shell crosslinked microsphere material | |
| CN108452813A (en) | A kind of MoS2/SrFe12O19The preparation method of composite magnetic photochemical catalyst | |
| CN107138160B (en) | Preparation method and application of nano zero-valent iron/titanium dioxide nanowire/graphene magnetic composite material | |
| CN109174161A (en) | It can Magneto separate TNTs/g-C3N4The preparation method and application of nanocomposite | |
| CN108745289A (en) | The preparation method and application of LDH and SWCNT nanocomposites | |
| CN103480323B (en) | A kind of method of one-step synthesis hierarchy tri-iron tetroxide microballoon with and products thereof application process | |
| CN106186158A (en) | Two selenizing molybdenums/ferroferric oxide magnetic nano composite, Preparation Method And The Use | |
| Zheng et al. | Binary solvent controllable synthesis of BiOCl towards enhanced photocatalytic activity | |
| CN108144592B (en) | Superparamagnetic composite nanoparticle, preparation method thereof and method for efficiently and selectively recovering phosphate | |
| CN106378111B (en) | A kind of magnetic Fe with nucleocapsid3O4/ PMMA nano-compound adsorbents and preparation method thereof | |
| CN106390933B (en) | Magnetic fluorination adsorbent of selective absorption perfluoro octyl sulfonic acid salt and its preparation method and application | |
| CN108993431A (en) | A kind of humic acid Modified clay mineral adsorbent and preparation method thereof | |
| CN102031506B (en) | Preparation method and application of Ni-P micro-nanometer material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160427 Termination date: 20190903 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |