CN110013827A - Crystalline state diatomite loading nanometer Fe3O4The difunctional magnetic adsorbent of Large ratio surface and preparation method thereof - Google Patents
Crystalline state diatomite loading nanometer Fe3O4The difunctional magnetic adsorbent of Large ratio surface and preparation method thereof Download PDFInfo
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- CN110013827A CN110013827A CN201910292272.6A CN201910292272A CN110013827A CN 110013827 A CN110013827 A CN 110013827A CN 201910292272 A CN201910292272 A CN 201910292272A CN 110013827 A CN110013827 A CN 110013827A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003463 adsorbent Substances 0.000 title claims abstract description 50
- 238000011068 loading method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 230000000694 effects Effects 0.000 claims abstract description 24
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000007605 air drying Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000001723 curing Methods 0.000 claims abstract description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 150000001450 anions Chemical class 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000005909 Kieselgur Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 229920000831 ionic polymer Polymers 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of crystalline state diatomite loading nanometer Fes3O4The difunctional magnetic adsorbent of Large ratio surface and preparation method thereof, belong to Heavy Metal Pollution Control technical field.The crystalline state diatomite that the present invention selects purity low does carrier, in the case where being not necessarily to protective atmosphere, being not necessarily to organic modification, be not necessarily to roasting, is prepared for crystalline state diatomite loading nanometer Fe by controlling synthesis condition using coprecipitation3O4The difunctional magnetic adsorbent of Large ratio surface, preparation method includes the crystalline state diatomite-molysite-ferrous salt mixed liquor for configuring specific molar ratio, the preparation of composite precursor, curing, Magnetic Isolation, washing, forced air drying, slight grinding.The invention synthesis technology is environmentally friendly, it is simple it is controllable, low in cost, be readily produced.The crystalline state diatomite loading nanometer Fe of synthesis3O4The difunctional magnetic adsorbent of Large ratio surface, 5~30 μm of partial size, 70~140m of specific surface area2/ g, magnetic great Yi recycling, either to Cu2+、Cd2+、VO3 ‑、Cr2O7 2‑Single Pollution liquid, or to the complicated contaminated liquid that these four zwitterions coexist, the effect administered simultaneously to anions and canons is all very excellent.
Description
Technical field
The invention discloses a kind of crystalline state diatomite loading nanometer Fes3O4The difunctional magnetic adsorbent of Large ratio surface and its
Preparation method belongs to Heavy Metal Pollution Control technical field.
Background technique
With the very fast development of industry and the quickening of urbanization process, more and more industrial pollutants are discharged into ring
In border, wherein being particularly acute with heavy metal-polluted water problem, that representative is Cu2+、Cd2+、Pb2+、Hg+Equal cations
The heavy metal pollution of form and VO3-、VO4 3-、Cr2O7 2-、CrO4 2-The heavy metal pollution of equal anionic forms.These two types pollution
Waste water toxicity generally all with higher and refractory organics, are discharged into after environment and often form what yin, yang polyion coexisted
Complicated heavy metal-polluted water, heavy metal contaminants alternating movement between each medium of the inside are formed dirty to the persistence of environment
Dye also can life to the mankind and the serious threat of health composition while seriously endangering the ecosystem.Therefore, how section
Efficiently solve the complicated heavy metal-polluted water that a variety of anions and canons coexist and become more and more important to the harm of environment and the mankind,
Have become countries in the world simultaneously and vast environmental scientific research worker studies one of the hot spot of concern.
The method administered at present for heavy metal contaminants in water mainly have chemical precipitation method, membrane separation process, electrolysis method, from
Sub- exchange process and absorption method.In these methods, absorption method is a kind of the most commonly used method, with it is efficient, easy to operate,
The selective good and reusable advantage of adsorbent.Absorption method administers the heavy metal that soluble yin, yang polyion coexists at present
The main policies of pollutant are step-by-step processing methods, i.e., first with a kind of one of adsorbent material selective absorption waste water electrical property
Ion then selects the ion of another adsorbent material absorption opposite-sign again.As using the adsorption material for being rich in acid centre
Material removal cation, then anion is removed with the adsorbent material containing basic center, this method is for simple ionic system
It is effective.But for the complex aqueous solution system that yin, yang polyion coexists, because strong by humic acid concentration, pH value, ion
The various factors such as the circulation of degree, temperature and dissolved oxygen influence, and charge mass transfer, hydrogen bond can occur between different ions and different groups
Effect, hydrophobic effect etc. cause anions and canons that absorption/complexing, desorption release and Transport And Transformation etc. occur on the adsorbent material multiple
Miscellaneous variation, therefore be difficult to obtain satisfied clean-up effect.In addition, stepwise adsorption facture, adsorption reaction, separation and recycled
Journey repeats, and takes time and effort at high cost.Therefore, the material for developing while having difunctional activated adoption site, is allowed to both have
Have Anion-adsorption site and meanwhile also have certain cationic adsorption site, then may be implemented in waste water anions and canons it is same
When adsorbing and removing, to reach the ideal regulation effect to heavy metal pollution liquid.
It but will be in acid that the same adsorbent material surface keeps charge opposite, alkali site " peaceful coexistence ", it is necessary to first solve
Certainly between each other it is spontaneous it is compound caused by active site and problem, be otherwise difficult to obtain good effect.To realization pair
The purpose of anions and canons while adsorbing and removing in heavy metal-polluted dye liquor, we must research and develop satisfactory difunctional adsorption material
Material.
Nanometer Fe3O4It as a kind of emerging adsorbent material, has many advantages, such as large specific surface area, reactivity are high
Etc. characteristics, be easily achieved separation and recovery especially with its magnetic susceptibility.But nanometer Fe3O4Exist in use easy to reunite
The problems such as low with adsorption capacity, therefore domestic and foreign scholars have done many researchs in terms of its modification.Such as with carboxyl, amine
The functional groups modification such as base, sulfydryl, hydroxyl, wherein amido functional group modifies Fe3O4Adsorbent is considered as most effective one
Kind because it can by electrostatic adsorption remove anionic species heavy metal ion, also can by complexing remove sun from
Subclass heavy metal ion.But nanometer Fe3O4The generally existing complex process of modification, it is at high cost, new environmental pollution can be generated
The defects of problem, limits its application and promotes.
Natural diatomaceous earth is chiefly used in administering with the heavy metal-polluted of cationic form migration as a kind of traditional adsorbent
Dye.Natural diatomaceous earth is that a kind of siliceous rock formed is deposited by the remains of diatom, has special porous structure, chemical component master
If SiO2, there is fine and smooth, loose, light, porous, water imbibition and the strong property of permeability.3.2 hundred million tons of China's diatomite reserves,
Prospective reserves is concentrated mainly on East China and the Northeast up to more than 20 hundred million tons, wherein larger has Jilin, Zhejiang, Yunnan, mountain
East, Sichuan Province etc..Though diatomite distribution is wide, high-quality diatomite concentrates merely on Changbai, Yunnan diatomite mining area, color
It is white, it is unbodied SiO2(SiO280% or more is usually accounted for, is reached as high as 94%), because it is with high purity and high surface activity excellent
Gesture and favor by researcher, substantially conduct a research around it.The diatomite in Miyi, Sichuan, China county is in light yellow, is crystalline state
SiO2(SiO2Mass fraction about 65%~75%), it is 3~4 grades of soil, optical purity is not low and surface-active is low, so added value
Low, deep processing has little significance.
Magnetic diatomite is increasingly becoming a kind of new adsorbent of everybody concern in recent years, has gathered nanometer Fe3O4With
The double dominant of diatomite.Such as a kind of magnetic diatomite base adsorbent and its preparation method and application (publication number
CN103432986A diatomite is pre-processed with acid solution), the pre- modification of physics is carried out with plasma, with ferrous ion pair
Diatomite impregnate modified, adds alkali to adjust pH and generates magnetic presoma, drying, roasting, grinding obtain modification infusorial earth
For Adsorption of Nitrobenzene from Aqueous Solution, the processes such as pickling, the pre- modification of plasma, roasting in the preparation process are obviously both unfavorable for environmental protection, energy
It consumes also higher.As magnetic diatomite adsorbant and the preparation method and application thereof (publication number CN104826579A) using diatomite as
Nucleome, surface coated ferriferrous oxide shell layer, preparation method include preparing containing diatomite mixed solution, on diatomite surface
It deposits ferroso-ferric oxide, carry out to the ferroso-ferric oxide of deposition aging, washing, vacuum drying, break process, the preparation
Technique is relatively simple, but needs vacuum condition, and prepared magnetic adsorbent has preferable absorption to the copper ion of cationic form
Effect.The present Research of magnetism diatomite is as follows at present: one, same magnetic adsorbent administers yin, yang polyion and complicated weight coexists
The example of metallic pollution water solution system is not reported at present, it is common that heavy metal-polluted to single anion or single cation
Dye system；Two, high-purity, unformed diatomite are because of high surface activity and the favor by researcher, low-purity, crystalline state diatom
Soil be nobody shows any interest in, nanometer Fe3O4The unmanned concern of coupling effect difference between different shape diatomite；Three, acid processing or organic
The preparation sections such as modification can generate new problem of environmental pollution；Four, protective atmosphere, hydrothermal synthesis, medium temperature calcining etc. are more multiple
Miscellaneous preparation method and process, it is clear that increase production cost.
In conclusion research and development do carrier with crystalline state diatomite, preparation process is environmentally friendly, it is simple it is controllable, low in cost, be easy to raw
Produce, to yin, yang heavy metal ion have excellent regulation effect difunctional magnetic adsorbent be it is what important, necessarily have
Wide application prospect.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of crystalline state diatomite loading nanometer Fes3O4Compare table greatly
Difunctional magnetic adsorbent in face and preparation method thereof.The difunctional magnetic adsorbent is carrier, preparation process with crystalline state diatomite
It is environmentally friendly, simple it is controllable, low in cost, be readily produced, either to Cu2+、Cd2+、VO3 -、Cr2O7 2-Single Pollution liquid, also
It is the complicated contaminated liquid that these four zwitterions are coexisted, the effect of improvement is all very excellent.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
Crystalline state diatomite loading nanometer Fe3O4The difunctional magnetic adsorbent of Large ratio surface and preparation method thereof, the preparation
Method the following steps are included:
(1) molysite of load weighted certain mol proportion and ferrous salt are dissolved in deionized water respectively and obtain iron salt solutions and Asia
The two is mixed to get mixed solution A by iron salt solutions；
(2) crystalline state diatomite is selected, mixed solution A is added into, is persistently stirred in constant temperature (30 DEG C~70 DEG C of temperature range)
Mix down the sodium hydroxide solution that a certain concentration (concentration range 1.0mol/L~2.0mol/L) is slowly added dropwise, pH value of solution to 9~10
When, composite precursor preparation could be completed；
(3) composite precursor of acquisition is cured in constant temperature (30 DEG C~70 DEG C of temperature range) water-bath 30min~
It after 60min, is separated by solid-liquid separation using additional magnet, deionized water is washed to neutrality, forced air drying, is slightly ground up to crystalline state
Tripolite loading nano Fe3O4The difunctional magnetic adsorbent of Large ratio surface.
In the step (1), in mixed solution A, the molar ratio of the molysite and ferrous salt is 1:1~2:1.
In the step (2), in crystalline state diatomite-molysite-ferrous salt mixed solution, crystalline state diatomite and iron
The total weight ratio of both salt and ferrous salt is 1:1.086~1:10.86.
In the step (3), the temperature range of forced air drying is 50 DEG C~60 DEG C, drying time 8h~12h.
In the step (2) and (3), in the preparation process such as precursor preparation, curing, drying under air conditions,
It is protected without particular atmosphere.
The crystalline state diatomite loading nanometer Fe3O4The difunctional magnetic adsorbent of Large ratio surface grain diameter be 5~30
μm, specific surface area is 70~140m2/ g, pore volume are 0.1~0.8cm3/ g, either to Cu2+、Cd2+、VO3 -、Cr2O7 2-'s
Single Pollution liquid, or to the complicated contaminated liquid that these four zwitterions coexist, regulation effect is all very excellent.
Beneficial effects of the present invention:
The present invention using low-purity, crystalline state diatomite as carrier, acidless treatment, unprotect atmosphere, without organic modification,
Under conditions of roasting etc., crystalline silicon is successfully synthesized with environmentally friendly, simple preparation process that is controllable, low in cost, being readily produced
Diatomaceous earth loading nanometer Fe3O4The difunctional magnetic adsorbent of Large ratio surface, either to Cu2+、Cd2+、VO3 -、Cr2O7 2-List
One contaminated liquid, or to the complicated contaminated liquid that these four zwitterions coexist, regulation effect is all very excellent.And this is difunctional
Magnetic adsorbent is to cationic Cu2+、Cd2+The mechanism of action be Electrostatic Absorption, to anion VO3 -、Cr2O7 2-The mechanism of action be
Neutralization problem is not present in the Electrostatic Absorption that redox reaction causes, two kinds of active sites " peaceful coexistence ", therefore real simultaneously
The difunctional absorption of heavy metal anions and canons is showed, which necessarily has broad application prospects.
Detailed description of the invention:
Fig. 1 is 1 crystalline state diatomite loading nanometer Fe of the embodiment of the present invention3O4Large ratio surface difunctional magnetic adsorbent
XRD spectra；
Fig. 2 is 1 crystalline state diatomite loading nanometer Fe of the embodiment of the present invention3O4Large ratio surface difunctional magnetic adsorbent
SEM photograph；
Fig. 3 is that the crystalline state diatomite of the embodiment of the present invention 1 and amorphous silicon diatomaceous earth do the suction of magnetism prepared by carrier respectively
Attached dose to Cu2+、Cd2+、VO3-、Cr2O7 2-The adsorption effect of Single Pollution liquid compares；
Fig. 4 is the crystalline state diatomite loading nanometer Fe prepared under the different synthesis temperatures of the embodiment of the present invention 23O4Compare table greatly
The difunctional magnetic adsorbent in face, to Cu2+、Cd2+、VO3-、Cr2O7 2-The adsorption effect comparison that complicated contaminated liquid coexists of ion.
Specific embodiment:
More preferably to illustrate effect of the invention, it is described further with reference to the accompanying drawings and examples.
Embodiment 1
Firstly, pressing n (Fe3+)/n(Fe2+) molar ratio be 2:1 weigh nine water ferric nitrate of 4.04000g and seven water of 1.39025g
Ferrous sulfate is dissolved in deionized water respectively and obtains iron nitrate solution and ferrous sulfate solution, the two is mixed
Solution A.Mixed solution A is separately added into 0.5g crystalline state diatomite and amorphous silicon diatomaceous earth for double, is placed on 50 DEG C of high-power constant temperature
It is mixed evenly on magnetic stirring apparatus, 1.0mol/L sodium hydroxide solution is slowly added dropwise under 50 DEG C of constant temperature stir, theory is used
Amount measures mixed solution pH after dripping is 10.It moves back in continuing constant temperature stirring 30min on magnetic stirring apparatus to 50 DEG C of water-baths
40min is cured in pot, is then realizing separation of solid and liquid outside plus under magnetic field condition.By washing of precipitate to neutrality, in 60 DEG C of electric heating drums
Dry 12h, slightly grinds up to crystalline state diatomite loading nanometer Fe in wind thermostatic drying chamber3O4Magnetic adsorbent and amorphous state
Tripolite loading nano Fe3O4Magnetic adsorbent.
By loading nanometer Fe3O4The crystalline state diatomite and amorphous silicon diatomaceous earth of front and back remove processing Cu respectively2+、Cd2+、VO3-、
Cr2O7 2-Single Pollution liquid, compare its regulation effect.Adsorption process is as follows: weighing 0.1g loading nanometer Fe respectively3O4Front and back
Crystalline state diatomite and amorphous silicon diatomaceous earth (4 parts every kind, totally 16 parts), sequentially add the Cu of 25mL a certain concentration (being specifically shown in Table 1)2 +、Cd2+、VO3 -、Cr2O7 2-In Single Pollution liquid, standing adsorption is centrifugated afterwards for 24 hours at room temperature, takes 5.0mL supernatant, is used
Inductive coupling plasma emission spectrograph detection, the results are shown in Table 1.
As the result is shown: compared with natural diatomaceous earth, loading nanometer Fe3O4Crystalline state diatomite and amorphous silicon diatomaceous earth pair afterwards
Cu2+、Cd2+、VO3 -、Cr2O7 2-The treatment effect of Single Pollution liquid is promoted significant；With loading nanometer Fe3O4Amorphous state diatom afterwards
Soil is compared, loading nanometer Fe3O4Crystalline state diatomite afterwards is to Cu2+、Cd2+Regulation effect it is very excellent, crystalline state carrier is slightly better than one
It raises, but to VO3 -、Cr2O7 2-Then different, crystalline state carrier is substantially better than amorphous state carrier.
1 loading nanometer Fe of table3O4Front and back crystalline state diatomite and amorphous silicon diatomaceous earth
To Cu2+、Cd2+、VO3-、Cr2O7 2-The adsorption effect of Single Pollution liquid compares
Embodiment 2
Firstly, pressing n (Fe3+)/n(Fe2+) molar ratio be 2:1 weigh nine water ferric nitrate of 4.04000g and seven water of 1.39025g
Ferrous sulfate is dissolved in deionized water respectively and obtains iron nitrate solution and ferrous sulfate solution, the two is mixed
Solution A.Mixed solution A sequentially adds 5 parts of 0.5g crystalline state diatomite in mixed solution A for 5 parts, respectively at 30 DEG C, 40 DEG C,
50 DEG C, 60 DEG C, stirring constant temperature is uniformly mixed in 70 DEG C of high-power constant temperature blender with magnetic force, then under the stirring of corresponding temperature constant temperature
1.5mol/L sodium hydroxide solution is slowly added dropwise and generates Fe3O4Precipitating, theoretical amount measures mixed solution pH after dripping is 9
~10.It is moved back in continuation corresponding temperature constant temperature stirring 30min on magnetic stirring apparatus and cures 50min into corresponding temperature water-bath,
Then separation of solid and liquid is being realized outside plus under magnetic field condition, it is dry in 60 DEG C of Constant Temp. Ovens by washing of precipitate to neutrality
10h slightly grinds up to the crystalline state diatomite loading nanometer Fe prepared under different synthesis temperatures3O4The difunctional magnetic of Large ratio surface
Property adsorbent.
The crystalline state diatomite loading nanometer Fe that will be prepared under 5 kinds of synthesis temperatures3O4The difunctional magnetic adsorbent of Large ratio surface
Processing Cu is removed respectively2+、Cd2+、VO3 -、Cr2O7 2-Single Pollution liquid and these four ions COMPLEX MIXED contaminated liquid, compare it
Regulation effect.Adsorption process is as follows: the crystalline state diatomite loading nanometer Fe that will be prepared under 5 kinds of synthesis temperatures3O4Large ratio surface it is double
Functional magnetic adsorbent respectively takes 5 parts, every part of 0.1g, and totally 25 parts；Sequentially adding 25mL a certain concentration, (specific concentration is shown in Table 2 and table
3) Cu2+、Cd2+、VO3 -、Cr2O7 2-Single Pollution liquid and these four ions COMPLEX MIXED contaminated liquid.It stands at room temperature
Absorption is centrifugated afterwards for 24 hours, is taken 5.0mL supernatant, is detected with inductive coupling plasma emission spectrograph, the results are shown in Table 2
With table 3.
The result shows that: the crystalline state diatomite loading nanometer Fe prepared under different synthesis temperatures3O4The difunctional magnetic of Large ratio surface
Property adsorbent, either to Cu2+、Cd2+、VO3 -、Cr2O7 2-Single Pollution liquid, or answer what these four zwitterions coexisted
Miscellaneous contaminated liquid, regulation effect are all very excellent.
The difunctional magnetic adsorbent prepared under the different synthesis temperatures of table 2
To Cu2+、Cd2+、VO3 -、Cr2O7 2-The adsorption effect of Single Pollution liquid compares
The difunctional magnetic adsorbent prepared under the different synthesis temperatures of table 3
To Cu2+、Cd2+、VO3 -、Cr2O7 2The adsorption effect comparison of COMPLEX MIXED contaminated liquid coexists in four kinds of ions
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, belongs to the scope of protection of the invention.
Claims (10)
1. crystalline state diatomite loading nanometer Fe3O4The difunctional magnetic adsorbent of Large ratio surface and preparation method thereof, including as load
The crystalline state diatomite of body and the nanometer Fe for being supported on diatomite surface3O4。
2. crystalline state diatomite loading nanometer Fe as described in claim 13O4The difunctional magnetic adsorbent of Large ratio surface, it is special
Sign is: the diatomite is crystalline state, predominantly disk algae, coronal algae etc., SiO2Mass fraction is 65%~75%, in pale yellow
Color, 15~30m of specific surface area2/ g, pore volume are 0.1~0.8cm3/g。
3. crystalline state diatomite loading nanometer Fe as described in claim 13O4The difunctional magnetic adsorbent of Large ratio surface, it is special
Sign is: the loaded article is nanometer Fe3O4, 18~25nm of partial size, carrying magnetic.
4. crystalline state diatomite loading nanometer Fe as described in claim 13O4The difunctional magnetic adsorbent of Large ratio surface, it is special
Sign is: the crystalline state diatomite and nanometer Fe3O4Weight ratio be 0.43~4.31.
5. crystalline state diatomite loading nanometer Fe as described in claim 13O4The difunctional magnetic adsorbent of Large ratio surface, it is special
Sign is: the grain diameter of the difunctional magnetic adsorbent of Large ratio surface is 5~30 μm, and specific surface area is 70~140m2/ g,
Pore volume is 0.1~0.8cm3/g。
6. crystalline state diatomite loading nanometer Fe3O4The difunctional magnetic adsorbent of Large ratio surface preparation method, including walk as follows
It is rapid:
(1) molysite of load weighted certain mol proportion and ferrous salt are dissolved in deionized water respectively and obtain iron salt solutions and ferrous salt
The two is mixed to get mixed solution A by solution；
(2) crystalline state diatomite is selected, mixed solution A is added into, under constant temperature (30 DEG C~70 DEG C of temperature range) persistently stirring
It is slowly added dropwise the sodium hydroxide solution of a certain concentration (concentration range 1.0mol/L~2.0mol/L), it is multiple when pH value of solution is to 9~10
Closing precursor preparation could complete；
(3) composite precursor of acquisition is cured to 30min~60min in constant temperature (30 DEG C~70 DEG C of temperature range) water-bath
Afterwards, it is separated by solid-liquid separation using additional magnet, deionized water is washed to neutrality, forced air drying, is slightly ground up to crystalline state diatom
Native loading nanometer Fe3O4The difunctional magnetic adsorbent of Large ratio surface.
7. crystalline state diatomite loading nanometer Fe as claimed in claim 63O4The difunctional magnetic adsorbent of Large ratio surface preparation side
Method, it is characterised in that: in mixed solution A, the molar ratio of the molysite and ferrous salt is 1:1~2:1；The crystalline state diatom
In soil-molysite-ferrous salt mixed solution, the total weight ratio of both crystalline state diatomite and molysite and ferrous salt is 1:1.086
~1:10.86.
8. crystalline state diatomite loading nanometer Fe as claimed in claim 63O4The difunctional magnetic adsorbent of Large ratio surface preparation side
Method, it is characterised in that: the temperature range of forced air drying is 50 DEG C~60 DEG C, drying time 8h~12h.
9. crystalline state diatomite loading nanometer Fe as claimed in claim 63O4The difunctional magnetic adsorbent of Large ratio surface preparation side
Method, it is characterised in that: in the preparation process such as precursor preparation, curing, drying under air conditions, protected without particular atmosphere
Shield.
10. crystalline state diatomite loading nanometer Fe a method as claimed in any one of claims 1 to 53O4The difunctional magnetic absorption of Large ratio surface
The crystalline state diatomite loading nanometer Fe of agent or the preparation method preparation as described in claim 6-9 is any3O4The double function of Large ratio surface
Energy magnetic adsorbent, either to Cu2+、Cd2+、VO3 -、Cr2O7 2-Single Pollution liquid, or these four zwitterions are coexisted
Complicated contaminated liquid, the effect of improvement is all very excellent.
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