CN106492714A - The preparation and application of calcium alginate coated Nanoscale Iron microsphere - Google Patents

The preparation and application of calcium alginate coated Nanoscale Iron microsphere Download PDF

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CN106492714A
CN106492714A CN201610969701.5A CN201610969701A CN106492714A CN 106492714 A CN106492714 A CN 106492714A CN 201610969701 A CN201610969701 A CN 201610969701A CN 106492714 A CN106492714 A CN 106492714A
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iron
microsphere
calcium
alginate
calcium alginate
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胡敬平
王安琪
侯慧杰
刘冰川
张鹏
武龙胜
李玲
黎建峰
胡少刚
汪东亮
杨家宽
梁莎
吴旭
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Huazhong University of Science and Technology
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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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen

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Abstract

The invention discloses a kind of preparation and application of calcium alginate coated Nanoscale Iron microsphere, wherein prepare and comprise the following steps：(1) reducing agent is dropped in soluble iron saline solution, obtains nano zero valence iron head product；Then, the inorganic salt impurities in the head product are removed, nano-iron material is obtained；(2) with water as dispersant, the nano-iron material that alginate and step (1) are obtained is dispersed in water to form disperse system；(3) disperse system is added in syringe, aqueous solution using soluble calcium salt is used as reception solution, the disperse system in syringe is made to project in reception solution based on electrostatic spinning technique, so as to form the microsphere for obtaining that calcium alginate wraps up Nanoscale Iron, i.e. calcium alginate coated Nanoscale Iron microsphere.The present invention by being improved to crucial cladding process design, can effectively solve the problem that nano zero valence iron easily reunite, oxidizable problem, preparation method is simple to operate, with low cost.

Description

The preparation and application of calcium alginate coated Nanoscale Iron microsphere
Technical field
The invention belongs to coated nano-iron material technical field, receives more particularly, to a kind of calcium alginate coated The preparation method of rice ferrum microsphere and application, the preparation of the calcium alginate coated Nanoscale Iron microsphere is based on electrostatic spinning microsphere Method, the calcium alginate coated Nanoscale Iron microsphere for preparing (that is, calcium alginate-Nanoscale Iron nucleocapsid structure, CA-Fe NPs, It is, nanometer iron surface by calcium alginate cover and formed nucleocapsid structure) can be applicable to degrade environment in organic contamination Thing.
Background technology
Nanotechnology is curbed environmental pollution and is constantly subjected to domestic and international extensive concern, and wherein nano zero valence iron is because of surface activity High, reducing power is strong, reaction rate is high, there is innocuousness and be widely applied in the middle of environmental pollution improvement.Nano zero valence iron (that is, nanoscale zero-valent iron, nZVI) refers to that particle diameter is in nanoscale and the ferrum between 1～100nm, leads to Often products therefrom is reduced for ferric ion.Nano zero valence iron has unique nucleocapsid dual structure, and its core is Zero-valent Iron Fe (0) the oxidation shell of layer, in metallic iron body-centered cubic crystal structure, is coated around Zero-valent Iron, is FeOOH (FeOOH).
Nano zero valence iron is larger to the removal capacity of pollutant, efficiency is higher, goes depollution advantage with distinct, in dye Boundless application prospect is shown in the removal of the pollutant such as material, heavy metal, nitrate, halogenated organic matters.Especially in drop In terms of solution chloro pollutant, nano zero valence iron degradation effect is notable.However, due to nano zero valence iron have oxidizable, reunite Shortcoming, it is suppressed that its reactivity, reduces its degradation efficiency to pollutant, greatly limit the technology in environmental improvement Application.
On the other hand, as the Typical Representative of halo organic pollution, trichloro ethylene (TCE) has bio-toxicity, antibiosis Thing degradability and long residual property, the serious health for threatening the mankind affect life, the production of the mankind.Traditional administering method has life Object space method, physical method and chemical method, biological method mainly have anaerobic biological process and aerobe method, all need electron donor or Additional co-metabolic substance, its defect are that the more difficult maintenances of pH, oxidation-reduction potential are difficult to control to, and microorganism easily produce poisonous Metabolite；Physical method mainly has aeration stripping method and active carbon adsorption, does not fundamentally remove TCE, easily produces Secondary pollution；Chemical method has electrochemical process, photocatalytic degradation method, chemical oxidization method, wherein chemical reduction method, chemical reduction method It is that the chlorine element of TCE is sloughed by electronation, and makes which become a kind of efficient, green of low toxicity even non-toxic degradation products Method, nowadays the principle exactly electronation of nano zero valence iron deoxidization, degradation TCE be subjected to domestic and international extensive concern.
For the shortcoming of the oxidizable and easy reunion of nano zero valence iron, nano zero valence iron is entered using the method for green non-pollution Row is modified, with improve its stability and catalytic performance be current nano zero valence iron research important directions.Specific means master There are bimetal nano material, Supported Nano Zero-valent Iron and coated Nanoscale Iron etc..Wherein, the nano iron particles of preparation are wrapped Wrap up in, its stability can be improved, extend its preservation and service life.Some researcheres adopt polymer wrapped nano-iron particle, Nanometer iron surface forms the integument of polymer, forms the nucleocapsid structure of Nanoscale Iron-polymer.These polymeric material antioxidation Performance is good, and it is oxidized to be effectively prevented nano zero valence iron, makes nano-iron particle that there is preferably thermodynamically stable property, and portion Divide polymeric material to have good selection to organo-chlorine pollutant, nano zero valence iron dechlorination can be strengthened.Although The nucleocapsid structure of Nanoscale Iron-polymer has good application effect, but the system of the nucleocapsid structure of general Nanoscale Iron-polymer Standby mode is complex, relatively costly, is unfavorable for actually used.
Content of the invention
Disadvantages described above or Improvement requirement for prior art, object of the present invention is to provide a kind of calcium alginate bag Preparation method and the application of type Nanoscale Iron microsphere is wrapped up in, wherein (by way of including cladding, is wrapped by cladding process design crucial to which Cover species, addition of material etc.) etc. be improved, can effectively solve the problem that compared with prior art nano zero valence iron easily reunite, Oxidizable problem, can strengthen its stability and controllability in the reaction, conveniently preserve and extend its service life, profit In practical application, and the present invention prepares calcium alginate parcel nano zero valence iron microsphere using method of electrostatic spinning, and preparation method is grasped Make simply, with low cost, using effect (such as degradation effect) is good.
For achieving the above object, according to one aspect of the present invention, there is provided a kind of calcium alginate coated Nanoscale Iron is micro- The preparation method of ball, it is characterised in that comprise the following steps：
(1) under protective atmosphere, by reproducibility higher than the reducing agent of ferrum simple substance, drop in soluble iron saline solution, institute Soluble ferric iron salt is stated at least one in solubility divalent iron salt and solubility trivalent iron salt, makes the soluble ferric iron salt molten Ferrous ion in liquid and/or ferric ion reduction, obtain nano zero valence iron head product；Then, remove in the head product Inorganic salt impurities, obtain nano-iron material；
(2) with water as dispersant, the nano-iron material that alginate and the step (1) are obtained is scattered in described Disperse system is formed in water；
(3) disperse system that the step (2) is obtained is added in syringe, using the aqueous solution of soluble calcium salt As solution is received, under protective atmosphere, the disperse system in the syringe is made to connect to described based on electrostatic spinning technique Receive in solution and project, so as to form the microsphere for obtaining that calcium alginate wraps up Nanoscale Iron, i.e. calcium alginate coated Nanoscale Iron microsphere.
As present invention further optimization, in step (3), positive voltage that the electrostatic spinning technique is adopted for 10kV, negative voltage are 0.
As present invention further optimization, in step (1), the reducing agent is sodium borohydride NaBH4, and boron Hydrofining KBH4In at least one, the soluble ferric iron salt be ferrous sulfate FeSO4, ferrous chloride FeCl2, iron sulfate Fe2 (SO4)3, and iron chloride FeCl3In at least one.
As present invention further optimization, in step (1), the amount of the material of the reducing agent is more than described solvable The amount of the material of property iron salt；Preferably, the soluble ferric iron salt is 1 with the ratio of the amount of the material of the reducing agent：(1～ 3)；
As present invention further optimization, in step (2), the alginate and the nano-iron material Mass ratio be 1:1.
As present invention further optimization, solubility calcium in the aqueous solution of soluble calcium salt described in step (3) The mass concentration of salt is (1～2) with the mass concentration ratio between two of alginate in disperse system described in the step (2)：1； Preferably, in the aqueous solution of the soluble calcium salt mass concentration of soluble calcium salt and alginate in the disperse system matter Amount both concentration is equal.
As present invention further optimization, in step (2), the alginate is sodium alginate and potassium alginate In at least one.
As present invention further optimization, in step (3), the soluble calcium salt is calcium chloride CaCl2, carbonic acid Hydrogen calcium Ca (HCO3)2With calcium acetate Ca (CH3COO)2In at least one.
Used as present invention further optimization, the protective atmosphere is at least one in nitrogen, helium and argon.
Used as present invention further optimization, the preparation method of the calcium alginate coated Nanoscale Iron microsphere also includes walking Suddenly：
(4) calcium alginate that the step (3) is formed is wrapped up the microsphere of Nanoscale Iron, centrifuge is first used, and It is separated by filtration and obtains solid；Then, then by these solids cleaned with deoxygenation ultra-pure water, and carried out normal-temperature vacuum drying, with The calcium ion or alginate of the microsphere surface residual of the calcium alginate parcel Nanoscale Iron is removed, so as to the sea after being cleaned Calcium alginate wraps up the microsphere of Nanoscale Iron, i.e. the calcium alginate coated Nanoscale Iron microsphere after cleaning.
It is another aspect of this invention to provide that the invention provides system using above-mentioned calcium alginate coated Nanoscale Iron microsphere Application of the calcium alginate coated Nanoscale Iron microsphere that Preparation Method is prepared in degradable organic pollutant；Preferably, described Calcium alginate coated Nanoscale Iron microsphere is used cooperatively with citrate, the calcium alginate coated Nanoscale Iron microsphere with described The mass ratio of both citrates is preferably 1：2, the citrate is micro- for dissolving the calcium alginate coated Nanoscale Iron Calcium alginate shell in ball.
Used as present invention further optimization, the organic pollution includes trichloro ethylene.
By the contemplated above technical scheme of the present invention, compared with prior art, due to being existed using electrostatic spinning technique Nano zero-valence iron surface prepares alginic acid calcium layer, makes calcium alginate parcel nano zero valence iron form calcium alginate coated Nanoscale Iron Microsphere, by controlling condition (the especially voltage of electrostatic spinning, the alginate in disperse system and the nanometer iron material of electrostatic spinning Concentration of material etc.), it can be ensured that the alginic acid calcium layer of formation is uniform, consistency of thickness.The calcium alginate coated Nanoscale Iron microsphere Particle diameter be 1～100 μm, (internal nanometer iron construction remains at nanometer at 0.2～20 μm for the THICKNESS CONTROL of alginic acid calcium layer Level).
Calcium alginate coated Nanoscale Iron microsphere (that is, the nano zero-valence for being wrapped up by calcium alginate that the present invention is prepared Ferrum microsphere, calcium alginate-nano zero valence iron nucleocapsid structure CA-Fe NPs), it is in protective atmosphere first with liquid phase reduction Under the conditions of prepare nano zero valence iron head product, then be based on electrostatic spinning technique, prepare microsphere using calcium alginate parcel Nanoscale Iron, Thus solve the problems, such as prior art prepare nano-iron material easily reunite, aoxidize, less stable, the calcium alginate bag for obtaining Type Nanoscale Iron microsphere good dispersion, good stability is wrapped up in, is highly suitable for degradable organic pollutant (e.g., trichloro ethylene etc.).
The present invention is added to a certain amount of well-mixed homogeneous material after syringe using electrostatic spinning Microspheres Technique, Under conditions of additional certain high direct voltage, the homogeneous material in syringe is continuous in the form of microsphere from straight peen or elbow, thin Close, rapidly be ejected to reception container in, receive container in can equipped with participate in microsphere reaction and be easy to microsphere preserve solution (such as CaCl2The solution containing calcium ion such as solution).This electrostatic spinning technique easily reunites for nano-particle, aoxidize scarce Fall into, Nanoscale Iron can be played uniformly, peptizaiton, prepare effect controllability by force, solve that its dispersibility is poor, utilization rate compared with Low problem.If also, by alginate coated Nanoscale Iron microsphere and citrate with the use of being applied to organic contamination The degraded of thing (such as trichloro ethylene TCE), can realize organic pollution by citrate to the dissolving of calcium alginate shell The Effective Regulation of degradation efficiency, the alginate coated Nanoscale Iron microsphere have higher degradation efficiency, and application prospect is good.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show Beneficial effect：
1st, the defect of nano-particle be easily reunite, oxidation, this makes, and its dispersibility is poor, utilization rate is relatively low, using Static Spinning Silk technology can play protection, peptizaiton to Nanoscale Iron；
2nd, calcium alginate coated Nanoscale Iron microsphere (the calcium alginate coated after including cleaning that the present invention is prepared Nanoscale Iron microsphere), i.e. calcium alginate gel wraps up nZVI, is kind of a calcium alginate nano zero valence iron nucleocapsid structure (CA-Fe NPs), be attached to nano zero-valence iron surface, degradable green and water-fast calcium alginate shell largely improve The non-oxidizability of nZVI, stability, facilitate nZVI to preserve；
3rd, it is applied in the degraded of TCE according to the CA-Fe NPs prepared by the inventive method, adds a certain amount of citric acid Salt dissolves can the calcium alginate shell of microsphere, can control degradation rate and effect by the amount of the different citrates of addition Rate, realizes the precise control of degradation rate and efficiency.As the amount for adding citrate is more, calcium alginate dissolving is faster, NZVI releases are more, and TCE degradation efficiencies are also higher.CA-Fe NPs are 1 with the mass ratio of sodium citrate:When 2, TCE highests are degraded Efficiency in 1h up to more than 80%, 4h up to more than 90%, 16h up to nearly 95%, degradation effect is good.
Description of the drawings
Fig. 1 is the Concentration-time of CA-Fe NPs material degradation TCE (concentration is 30mg/L) prepared by the embodiment of the present invention Figure；
Fig. 2 be the embodiment of the present invention prepare CA-Fe NPs material degradation TCE (concentration is 30mg/L) degradation efficiency- Time diagram.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, and It is not used in the restriction present invention.As long as additionally, involved technical characteristic in invention described below each embodiment Do not constitute conflict each other can just be mutually combined.
The invention provides a kind of preparation method of coated nano-iron material CA-Fe NPs, comprises the steps：
(1) in an inert atmosphere, by excessive sodium borohydride (NaBH4) drop to ferrous sulfate (FeSO4) in solution ( That is, the addition of reducing agent is preferably excessive state, it is ensured that the amount of the nano zero valence iron of generation；Can also can using other Soluble divalent iron salt or solubility ferric salt solution), nano zero valence iron head product is obtained, ferrous sulfate is excellent with sodium borohydride It is 1 to select concentration ratio:1～1:3 (when concentration ratio is less than 1:When 1, not exclusively, the amount for generating Nanoscale Iron is less, and concentration ratio is too high for reaction When, reaction rate is too fast, operation inconvenience, and relatively costly)；The impurity such as inorganic salt in the head product are removed, nanometer is obtained Iron material, then (that is, the uniform dispersion of homogeneous material is mixed to form with a certain amount of soluble alginate (e.g., sodium alginate) System), nano-iron material is 1 with the preferred mass ratio of sodium alginate:1, Nanoscale Iron now is more likely formed homogeneously with sodium alginate Material；The homogeneous material is added in elbow syringe, using soluble calcium solution, such as calcium chloride (CaCl2) be Solution is received, in an inert atmosphere, the microsphere that calcium alginate (CA) gel wraps up nZVI is obtained using method of electrostatic spinning, is obtained sea Calcium alginate nano zero valence iron nucleocapsid structure (CA-Fe NPs), calcium chloride (CaCl2) it is 1 with the preferred concentration ratio of sodium alginate: 1, now it is more likely formed microsphere；The inert atmosphere is one or more in nitrogen, helium or argon；
(2) head product of step (1) gained is separated by filtration and obtains solid first with centrifuge, then by the CA-Fe NPs materials are cleaned with deoxygenation ultra-pure water, and carry out normal-temperature vacuum drying, residual to remove the CA-Fe NPs material surfaces The CaCl for staying2Or sodium alginate.
The CA-Fe NPs materials can be used for degrade TCE, by the CA-Fe NPs materials of gained in step (2) with a certain amount of Sodium citrate solution mixes, and calcium alginate glue shell dissolving is released nZVI, so as to trichloro ethylene of degrading (TCE).Plus Entering a certain amount of sodium citrate dissolves can calcium alginate shell, can control to degrade by the amount of the different sodium citrates of addition Speed and efficiency.
It is below specific embodiment：
Embodiment 1
The present embodiment is comprised the following steps：
(1) under room temperature condition, by 5g green vitriol (FeSO4·7H2O) solid is dissolved in the 100mL deoxidation second that matches somebody with somebody In alcohol-water solution, (ethanol can be 1 with the volume ratio of water：4), the solution that ferrous sulfate concentration is 0.05g/mL is formed, and to which Middle addition 0.5g Polyethylene Glycol (PEG-2000) solid, stirs.Sodium borohydride (the NaBH of 2.8g is taken again4) in 20mL mass Percentage concentration is in 0.1% NaOH solution, obtains the NaBH that sodium borohydride concentration is 0.14g/mL after fully dissolving4Solution. In inert atmosphere, under mechanical agitation, with glue head dropper by NaBH4Solution is gradually added drop-wise to FeSO4In solution, obtain NZVI head products.NZVI solids after by centrifugation take out, and are cleaned with deoxidation ultra-pure water and be centrifuged after two to three times again, will separate The solid normal-temperature vacuum for going out is dried, and the i.e. nano-iron material (that is, zero-valent iron material) for obtaining, finally in inert atmosphere condition Lower sealing preserve；
(2) 0.1g sodium alginate powders are taken to be dissolved in 10mL deoxidation ultra-pure waters, is stirred and is dissolved to which, added obtained in 0.1g Nano-iron material, be sufficiently stirred for being mixed into homogeneous material (in the step, the mass concentration of alginate can also be other values, As long as by the quality control of the quality of alginate and Nanoscale Iron 1：1 or so, the mass concentration of soluble calcium salt (sees below Step 3) with the control of the mass concentration ratio between two of alginate 1～2：1, homogeneous material is formed to ensure)；
(3), during add homogeneous material to elbow syringe, 0.1g CALCIUM CHLORIDE DIHYDRATE (CaCl are taken2·2H2O) solid is molten In 10mL deoxygenation ultra-pure waters, (mass concentration of the soluble calcium salt can also be other values to solution, as long as concentration is in 0.01g/mL It is distributed in the range of～0.02g/mL), it is transferred in there-necked flask, as reception solution.In inert atmosphere, additional positive voltage Under conditions of 10kV, negative voltage 0V, CA-Fe NPs are prepared using electrostatic spinning Microspheres Technique.By obtained head product deoxidation Ultra-pure water cleaning one is to secondary, and carries out normal temperature drying, obtains dry CA-Fe NPs materials.
(4) 3 identical indigo plant mouth air-tight bottles are prepared, labelling 1,2,3 is added thereto to 100mL concentration respectively for 30mg/ The CA-Fe NPs that the TCE solution of L and 0.1g are prepared.0.05g, 0.10g, 0.20g lemon is separately added into again in 1,2, No. 3 bottles Lemon acid sodium.Using gas chromatography (GC) indirect determination TCE concentration and TCE degradation efficiencies are calculated, then draw concentration-time (TCEConcentration-Time) curve and degradation rate time (Degradation ratio-Time) curve, respectively such as Fig. 1 and Fig. 2 (in figure, SC represents sodium citrate).In figure, LP nZVI are that liquid phase reduction is obtained nano zero valence iron, i.e. this Bright prepare the nano-iron material (that is, zero-valent iron material) that obtains after the purification of nano zero valence iron head product.
The reducing agent prepared used in nano zero valence iron process in the present invention, except sodium borohydride NaBH4Outward, can be with Using other reducing agents, as long as the reproducibility of reducing agent is to enable to ferrous ion Fe2+(or iron ion Fe3+) it is reduced into 0 valency Ferrum Fe can be (if reproducibility is higher than the strong reductant of ferrum simple substance).Electrostatic spinning of the present invention its adopt device (bag Include electrode setting etc.) existing electrostatic spinning apparatus can be adopted, for example may include metallic nozzle (metallic nozzle and syringe Be connected), metallic cathode collecting board, receive solution can be located between metallic nozzle and metallic cathode collecting board, for example, it is possible to be located at In metallic cathode collecting board.Method of electrostatic spinning of the present invention, its positive voltage can be 10kV, and negative voltage can be 0, when Other voltages can also be adopted so, as long as the disperse system in syringe can be injected in reception solution.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not in order to The present invention, all any modification, equivalent and improvement that is made within the spirit and principles in the present invention etc. is limited, all should be included Within protection scope of the present invention.

Claims (9)

1. a kind of preparation method of calcium alginate coated Nanoscale Iron microsphere, it is characterised in that comprise the following steps：
(1) under protective atmosphere, by reproducibility higher than ferrum simple substance reducing agent, drop in soluble iron saline solution, described can Dissolubility iron salt is solubility divalent iron salt and at least one in solubility trivalent iron salt, makes in the soluble iron saline solution Ferrous ion and/or ferric ion reduction, obtain nano zero valence iron head product；Then, remove inorganic in the head product Salt impurity, obtains nano-iron material；
(2) with water as dispersant, the nano-iron material that alginate and the step (1) are obtained is scattered in the water Form disperse system；
(3) disperse system that the step (2) is obtained is added in syringe, using the aqueous solution conduct of soluble calcium salt Solution is received, under protective atmosphere, makes based on electrostatic spinning technique the disperse system in the syringe molten to the reception Project in liquid, so as to form the microsphere for obtaining that calcium alginate wraps up Nanoscale Iron, i.e. calcium alginate coated Nanoscale Iron microsphere.
2. the preparation method of calcium alginate coated Nanoscale Iron microsphere as claimed in claim 1, it is characterised in that the step (3), in, for 10kV, negative voltage is 0 to the positive voltage adopted by the electrostatic spinning technique.
3. the preparation method of calcium alginate coated Nanoscale Iron microsphere as claimed in claim 1, it is characterised in that the step (1), in, the reducing agent is sodium borohydride NaBH4, and potassium borohydride KBH4In at least one, the soluble ferric iron salt is Ferrous sulfate FeSO4, ferrous chloride FeCl2, iron sulfate Fe2(SO4)3, and iron chloride FeCl3In at least one.
4. the preparation method of calcium alginate coated Nanoscale Iron microsphere as claimed in claim 1, it is characterised in that the step (1), in, the amount of the material of the reducing agent is more than the amount of the material of the soluble ferric iron salt；Preferably, the soluble ferric iron salt Ratio with the amount of the material of the reducing agent is 1：(1～3)；
In step (2), the alginate is 1 with the mass ratio of the nano-iron material:1；
Described in step (3) in the aqueous solution of soluble calcium salt in the mass concentration of soluble calcium salt and the step (2) In the disperse system, the mass concentration ratio between two of alginate is (1～2)：1；Preferably, the soluble calcium salt is water-soluble In liquid, the mass concentration of soluble calcium salt is equal with the mass concentration of alginate in the disperse system.
5. the preparation method of calcium alginate coated Nanoscale Iron microsphere as claimed in claim 1, it is characterised in that the step (2), in, the alginate is at least one in sodium alginate and potassium alginate；
In step (3), the soluble calcium salt is calcium chloride CaCl2, calcium bicarbonate Ca (HCO3)2With calcium acetate Ca (CH3COO)2In at least one.
6. the preparation method of calcium alginate coated Nanoscale Iron microsphere as claimed in claim 1, it is characterised in that the shielding gas Atmosphere is at least one in nitrogen, helium and argon.
7. the preparation method of calcium alginate coated Nanoscale Iron microsphere as claimed in claim 1, it is characterised in that the alginic acid The preparation method of calcium coated Nanoscale Iron microsphere also includes step：
(4) calcium alginate that the step (3) is formed is wrapped up the microsphere of Nanoscale Iron, centrifuge is first used, and is filtered Isolated solid；Then, then by these solids cleaned with deoxygenation ultra-pure water, and carried out normal-temperature vacuum drying, to remove The calcium ion or alginate of the microsphere surface residual of the calcium alginate parcel Nanoscale Iron, so as to the alginic acid after being cleaned Calcium wraps up the microsphere of Nanoscale Iron, i.e. the calcium alginate coated Nanoscale Iron microsphere after cleaning.
8. it is prepared into using the preparation method of calcium alginate coated Nanoscale Iron microsphere as described in claim 1-7 any one To application of the calcium alginate coated Nanoscale Iron microsphere in degradable organic pollutant；Preferably, the calcium alginate parcel Type Nanoscale Iron microsphere is used cooperatively with citrate, the calcium alginate coated Nanoscale Iron microsphere and the citrate Mass ratio be preferably 1：2, the citrate is used for dissolving the alginic acid in the calcium alginate coated Nanoscale Iron microsphere Calcium shell.
9. application as claimed in claim 8, it is characterised in that the organic pollution includes trichloro ethylene.
CN201610969701.5A 2016-10-28 2016-10-28 The preparation and application of calcium alginate coated Nanoscale Iron microsphere Pending CN106492714A (en)

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CN109277083A (en) * 2018-10-26 2019-01-29 中国海洋大学 A kind of ferromagnetism charcoal ball of purifying water body and the preparation method and application thereof
CN110153170A (en) * 2019-05-23 2019-08-23 四川大学 Composite material, preparation method and application for heavy metal-organic matter reparation
CN110394160A (en) * 2019-08-27 2019-11-01 哈尔滨理工大学 The preparation method of spherical calcium alginate@FeOOH desulfurizing agent
CN110760309A (en) * 2019-11-29 2020-02-07 广西大学 Reducing agent for treating hexavalent chromium in soil and using method thereof
CN113101973A (en) * 2021-04-12 2021-07-13 天津城建大学 High-activity photochromic bismuth oxychloride/calcium alginate photocatalytic hydrogel microsphere and preparation method thereof
CN113666460A (en) * 2021-05-10 2021-11-19 中国海洋大学 Zero-valent metal loaded alginate-based carbon spheres and preparation method and application thereof
CN113713859A (en) * 2021-08-24 2021-11-30 上海应用技术大学 Ferric alginate-sodium citrate gel material and preparation method and application thereof
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CN110153170B (en) * 2019-05-23 2021-09-10 四川大学 Composite material for heavy metal-organic matter remediation, preparation method and application thereof
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CN110394160A (en) * 2019-08-27 2019-11-01 哈尔滨理工大学 The preparation method of spherical calcium alginate@FeOOH desulfurizing agent
CN110760309A (en) * 2019-11-29 2020-02-07 广西大学 Reducing agent for treating hexavalent chromium in soil and using method thereof
CN113101973A (en) * 2021-04-12 2021-07-13 天津城建大学 High-activity photochromic bismuth oxychloride/calcium alginate photocatalytic hydrogel microsphere and preparation method thereof
CN113101973B (en) * 2021-04-12 2022-09-09 天津城建大学 High-activity photochromic bismuth oxychloride/calcium alginate photocatalytic hydrogel microsphere and preparation method thereof
CN113666460A (en) * 2021-05-10 2021-11-19 中国海洋大学 Zero-valent metal loaded alginate-based carbon spheres and preparation method and application thereof
CN113713859A (en) * 2021-08-24 2021-11-30 上海应用技术大学 Ferric alginate-sodium citrate gel material and preparation method and application thereof
CN114029039A (en) * 2021-11-29 2022-02-11 陕西省中勘环境地质研究中心有限公司 Nano zero-valent iron gel ball, preparation method thereof and application of nano zero-valent iron gel ball in removing heavy metal ions
CN115769898A (en) * 2022-12-09 2023-03-10 西安交通大学 Zero-valent iron-based hydrogen-rich food enhancer and preparation method and application thereof

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