CN108031439A - A kind of magnetic retention chelate adsorption and preparation method thereof - Google Patents

A kind of magnetic retention chelate adsorption and preparation method thereof Download PDF

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CN108031439A
CN108031439A CN201711343181.8A CN201711343181A CN108031439A CN 108031439 A CN108031439 A CN 108031439A CN 201711343181 A CN201711343181 A CN 201711343181A CN 108031439 A CN108031439 A CN 108031439A
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ferroso
ferric oxide
magnetic retention
adsorption
preparation
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CN108031439B (en
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刘立华
赵露
杨正池
周智华
唐安平
薛建荣
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Hunan University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/28—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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
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    • C02F2101/20—Heavy metals or heavy metal compounds

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Abstract

The present invention relates to a kind of magnetic retention chelate adsorption and preparation method thereof.Epoxychloropropane is set to aggregate into linear polymer chain in the presence of ferroso-ferric oxide microballoon with triethylene tetramine first, original position absorption, be wrapped in ferroso-ferric oxide microsphere surface；It is then dispersed in toluene, adding glutaraldehyde makes macromolecular chain further be crosslinked, so as to stably be coated on ferroso-ferric oxide microsphere surface；Again in aqueous, carbon disulfide is made to modify dithiocarbonic acid base with the active amino on macromolecular chain or imino group reaction under sodium hydroxide catalyzed and generate magnetic retention chelate adsorption on the surface of ferroso-ferric oxide.The present invention is effectively by dithiocarbonic acid base, amino, imino group and hydroxyl isoreactivity base group modification to ferroso-ferric oxide microsphere surface, substantially increase the trapping adsorption capacity to heavy metal, and there is excellent Magneto separate performance, later separation is convenient, absorption, separation continuous operation can be achieved, easy to industrial applications with promoting.

Description

A kind of magnetic retention chelate adsorption and preparation method thereof
Technical field
The present invention relates to heavy metal containing wastewater treatment field, more particularly, to a kind of magnetic retention chelate adsorption and its system Preparation Method.
Background technology
Due to industry and the fast development of urbanization, the excess of heavy metal is discharged into environment and has caused in a global range Great environmental problem.Due to that can be degraded into innocuous substance unlike most organic pollutants, heavy metal cannot be biodegradable, and Human body can be finally run up to by food chain and finally produce cumulative poison, therefore, seriously endanger the health of people.Metal Plating, mineral selecting, process hides, chlorine industry, radiator manufacture, smelting, alloy and storage battery manufacturing industry etc. can all produce a large amount of Waste water containing a variety of heavy metals, such as cadmium, chromium, arsenic, copper, mercury, nickel, antimony, lead, manganese and zinc.These heavy metals are not only Health is seriously endangered, also results in huge economic loss, becomes and restricts international community and China's economy, social development and the people Raw improved significant problem.Although have developed various heavy wastewater treatment method so far, such as chemical precipitation method, ferrite Method, ion-exchange, floatation, membrane separating method, electrochemical method, absorption method etc., but all there are some shortcomings for these methods And deficiency, therefore, still lack blanket method.Comparatively speaking, absorption method is due to easy to operate, efficient, cost phase It is adaptable to use environment to relatively low, particularly suitable for the advanced treating of low concentration wastewater or waste water, therefore, give up in heavy metal Water treatment field is subject to increasingly extensive attention, it has also become a kind of very important process for treating heavy-metal waste water.
It is searching and research and development efficient absorption material using the most important task of Heavymetal Wastewater Treatment by Adsorption.Absorption method will Ask sorbing material that not only there is high adsorption capacity, longer service life cycle to heavy metal, but also require preferable Separating property, so as to continuous operation and industrial application.The adsorbance of sorbing material depends primarily upon sorbing material Specific surface area, surface active groups, its pore passage structure, pore size and its distribution etc. are further included for porous material.And separate Performance then depends primarily upon the granularity of sorbing material, density, and material in use whether easily broken refinement, swelling And solvation and be difficult to separate with solvent.At present, most sorbing materials are primarily present problems with：1. adsorption capacity is little；② It is higher to manufacture cost；3. zeolite regeneration is difficult, service life is short；4. separated after absorption heavy metal more difficult etc..Multinomial research table It is bright, dithiocarbonic acid base (- CSS—) contents of many kinds of heavy metal ion, such as Cd2+、Cu2+、Hg2+、Ni2+、Pb2+、Mn2+And Zn2+Deng having Good sequestering power.Magneto separate is a kind of easy to operate, easy to continuous operation separate mode, is obtained in separation process Increasingly extensive application.
The content of the invention
For existing sorbing material in terms of heavy metal containing wastewater treatment existing deficiency, and dithiocarbonic acid base (- CSS—) in terms of heavy metal chelating the advantages of and Magneto separate serialization advantage, a kind of magnetic retention chela of design construction of the present invention Close sorbing material, an object of the present invention, which is just to provide, a kind of has excellent heavy metal adsorption trapping ability and separating property concurrently Magnetic retention chelate adsorption, it is black solid powder, its structure is in the winding of magnetic ferroferric oxide microsphere surface, bag Cover dithiocarbonic acid the base (- CSS for being modified with and there is strong sequestering power to contents of many kinds of heavy metal ion—) macromolecular chain and formed Cage structure；Its main feature is that：(1) in the winding of magnetic ferroferric oxide particle, macromolecule of the parcel with various active group Chain, then modifies dithiocarbonic acid base onto macromolecular chain, forms a kind of kernel and enriches chela for magnetic-particle, appearance EDS maps Close the cage structure material of group；(2) synthetic material not only has heavy metal good chelating trapping performance, but also can pass through magnetic Field makes sorbing material conveniently be separated with handling water, therefore, it can be achieved that the serialization of adsorption separation process, so as to improve adsorbing separation Effect and efficiency, easy to heavy industrialization application.
Another object of the present invention is the preparation method for providing above-mentioned magnetic retention chelate adsorption, including following step Suddenly：
(1) it is 1: 40~50g/ml by ferroso-ferric oxide by ferroso-ferric oxide microballoon and polar organic solvent mass volume ratio Microballoon and polar organic solvent are added in reactor, are then by polyethylene polyamine and ferroso-ferric oxide microspheres quality ratio Add polyethylene polyamine at 1.5~3.0: 1, and ultrasonic wave Aided Machine stirs 2~3h；Then 50~60 DEG C are warming up to, by epoxy Epoxychloropropane is slowly added dropwise for 1.0~1.1: 1 in the ratio between amount of material of chloropropane and polyethylene polyamine, after being added dropwise to complete, 2~3h of reaction is further continued for, is cooled to room temperature, then solid matter is separated with magnet adsorption；
(2) step (1) obtained solid material is transferred in reactor, by ferroso-ferric oxide microballoon and the mass body of toluene Product for 1: 40~50g/ml than adding toluene, and ultrasonic wave Aided Machine stirs 2~3h, then by glutaraldehyde and polyethylene polyamine The ratio between the amount of material measure glutaraldehydes for 1: 8~10, be configured to the chloroformic solution that mass percentage concentration is 5~10%, slowly It is added in reactor, 2~4h is crosslinked at 60~80 DEG C；Room temperature is cooled to, is separated with magnet adsorption with solvent, is then distinguished With ethanol and distill water washing 3~5 times；
(3) step (2) obtained solid material is transferred in reactor, adds the steaming of 40~50 times of solid matter mass Distilled water, is then 2.2~3.9: 2.0~3.0 by the ratio between amount of material of sodium hydroxide, carbon disulfide and polyethylene polyamine: 1.0, first weigh sodium hydroxide and be added in reactor, measuring carbon disulfide again after to be dissolved is slowly dropped in reactor, adds The reaction was continued 3~5h after complete；Then 50~65 DEG C of 30~60min of reaction are warming up to, are cooled to room temperature, with magnet adsorption and solution Separation, then be washed with distilled water 3~5 times, it is drying to obtain magnetic retention chelate adsorption.
Further, a diameter of 200-500nm of ferroso-ferric oxide microballoon.
Further, polar organic solvent is absolute ethyl alcohol or tetrahydrofuran.
Further, polyethylene polyamine is triethylene tetramine or tetraethylenepentamine.
Further, the preferred three-necked bottle of reactor, more preferably with reflux condensing tube, constant pressure funnel and mechanical agitation The three-necked bottle of device.
Further, dry to be dried in vacuo, temperature is 40~50 DEG C.
Further, epoxychloropropane used, toluene, glutaraldehyde, chloroform, ethanol, sodium hydroxide and carbon disulfide are equal It is pure to analyze.
The present invention relates to a kind of magnetic retention chelate adsorption and preparation method thereof, first by ferroso-ferric oxide microballoon ultrasound Wavelength-division is dispersed in the polar organic solvent containing polyethylene polyamine, and it is linear high with triethylene tetramine generation to add epoxychloropropane Strand absorption, be wrapped in ferroso-ferric oxide microsphere surface, is then separated with magnet adsorption with reaction solution, is redispersed in non-pole In the toluene of property, the macromolecular chain for being wrapped in ferroso-ferric oxide microsphere surface is set further to be crosslinked by adding glutaraldehyde, so that Stably it is coated on ferroso-ferric oxide microsphere surface；Then in the presence of sodium hydroxide, make on carbon disulfide and macromolecular chain Active amino or imino group reaction and by the dithiocarbonic acid base for having strong sequestering power to contents of many kinds of heavy metal ion modify four The surface of Fe 3 O and generate magnetic retention chelate adsorption.It can will effectively contain amino, imino group and hydroxyl etc. The macromolecular chain of active group is stably coated on magnetic ferroferric oxide microsphere surface and forms cage structure, and by further Reaction modifies the dithiocarbonic acid base for having strong chelation to contents of many kinds of heavy metal ion to ferroso-ferric oxide microsphere surface, makes it Abundant chelating, coordinating group are contained in surface, substantially increase the trapping adsorption capacity to heavy metal, simultaneously as four oxidations Three-iron is rolled in macromolecule link network, it is also had excellent Magneto separate performance.Therefore, the present invention not only overcomes four oxidations Three-iron microsphere surface active group deficiency, it is poor to heavy metal adsorption the problem of, and solve sorbing material absorption a huge sum of money Separated after category cumbersome, it is impossible to the problem of operating continuously, it can be achieved that absorption, separation continuous operation, easy to industrial applications with Promote.
The present invention is possessed compared with prior art to be had the beneficial effect that：
(1) the method for the present invention first disperses ferroso-ferric oxide microballoon in polar organic solvent, then in ferroso-ferric oxide microballoon In the presence of, polyethylene polyamine is generated linear polymeric with epichlorohydrin reaction, original position winding, be wrapped in ferroso-ferric oxide Microsphere surface, then macromolecule link network is further cross-linked to form by the macromolecular chain that glutaraldehyde makes to be wrapped around in particle surface, Clad is set stably to be coated on ferroso-ferric oxide microsphere surface, hence it is evident that to improve the stability of sorbing material.Meanwhile by more sub- With epoxychloropropane polymerisation generation macromolecular chain occurs for polyethylene polyamine, effectively by hydroxyl, amino, imino group isoreactivity base Group's modification is in ferroso-ferric oxide microsphere surface, easy to be further converted into having heavy metal the dithiocarbonic acid of strong sequestering power Base.
(2) the method for the present invention disperses to have wound, after the ferroso-ferric oxide microballoon of adsorbed polymer chain in toluene, adds penta Dialdehyde is crosslinked, and is reduced water soluble polymer chain and is come off from microsphere surface, ensure that the amount of the macromolecular chain of cladding, so that It ensure that the quantity of active group.
(3) the method for the present invention using magnet adsorption separation be conducive to separate non-magnetic material, so as to get intermediate and Product is the material by macromolecular chain coated ferroferric oxide microballoon, reduces the interference of namagnetic substance, while make four oxygen Change three-iron microsphere surface wrapping layer evenly.
(4) product grain of the present invention is using magnetic ferroferric oxide microballoon as kernel, and surface is by containing abundant active group The cage structure that group's dithiocarbonic acid base, hydroxyl and amino, the macromolecule link network of imino group are formed, makes product have excellent chela The ability of trap heavy metals is closed, also with excellent Magneto separate performance, substantially increases the trapping adsorption capacity to heavy metal, and Efficiently solve separate after sorbing material absorption heavy metal it is cumbersome, it is impossible to the problem of operating continuously is, it can be achieved that heavy metal Efficiently removal and adsorbing separation continuous operation, easy to industrial application.
Brief description of the drawings
Fig. 1 is the preparation process FB(flow block) of the present invention；
Fig. 2 is the structure chart of magnetic retention chelate adsorption of the present invention；
Fig. 3 is the infrared spectrogram of 1 gained magnetic retention chelate adsorption of the embodiment of the present invention；
Fig. 4 is the transmission electron microscope picture of 1 gained magnetic retention chelate adsorption of the embodiment of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1
(1) 2.0g average grain diameters are taken to be added to 250mL's for the ferroso-ferric oxide microballoon and 100mL absolute ethyl alcohols of 430nm With in dropping funel, reflux condensing tube and churned mechanically three-necked bottle, it is 95.0% then to add 4.00g mass percentage concentrations Triethylene tetramine, ultrasonic wave Aided Machine stirring 3h.60 DEG C are warming up to, 2.4mL mass percentage concentrations, which are slowly added dropwise, is 99.0% epoxychloropropane, after being added dropwise to complete, is further continued for reaction 3h, is cooled to room temperature, then separate solids with magnet adsorption Matter.
(2) the isolated solid matter of step (1) be transferred to 250mL with dropping funel, reflux condensing tube and In churned mechanically three-necked bottle, 100mL toluene is added, ultrasonic wave Aided Machine stirring 3h, is then slowly dripped by dropping funel The chloroformic solution for adding the mass percentage concentration being configured to by 0.36mL glutaraldehydes to be 5.0%, reacts 3h after dripping at 70 DEG C； Room temperature is cooled to, is separated with magnet adsorption with solvent, ethanol is then used respectively and distills water washing 5 times.
(3) dropping funel, reflux condensing tube and machinery are carried what the solid matter that step (2) obtains was transferred to 250mL In the three-necked bottle of stirring, 110mL distilled water is added, adds 3.24g solid NaOH, after stirring and dissolving, is slowly added dropwise at room temperature Carbon disulfide 4.2mL, continues to stir 4h after adding, is then warming up to 60 DEG C, the reaction was continued 50min；It is cooled to room temperature, uses magnet Absorption is separated with solution, then is washed with distilled water 5 times, is placed in vacuum drying chamber in 40 DEG C that drying to constant weight, obtains magnetic retention Chelate adsorption 2.67g.
Embodiment 2
(1) 2.0g average grain diameters are taken to be added to the band of 250mL for the ferroso-ferric oxide microballoon and 90mL absolute ethyl alcohols of 340nm Have in dropping funel, reflux condensing tube and churned mechanically three-necked bottle, it is 95.0% then to add 4.50g mass percentage concentrations Triethylene tetramine, ultrasonic wave Aided Machine stirring 2.5h.55 DEG C are warming up to, 2.6mL mass percentage concentrations, which are slowly added dropwise, is 99.0% epoxychloropropane, after being added dropwise to complete, is further continued for reaction 2.5h, is cooled to room temperature, then separate solid with magnet adsorption Material.
(2) the isolated solid matter of step (1) be transferred to 250mL with dropping funel, reflux condensing tube and In churned mechanically three-necked bottle, 90mL toluene is added, ultrasonic wave Aided Machine stirring 2h, is then slowly added dropwise by dropping funel The chloroformic solution that the mass percentage concentration being configured to by 0.33mL glutaraldehydes is 7.0%, reacts 3h after dripping at 80 DEG C；It is cold But room temperature is arrived, is separated with magnet adsorption with solvent, ethanol is then used respectively and distills water washing 4 times.
(3) dropping funel, reflux condensing tube and machinery are carried what the solid matter that step (2) obtains was transferred to 250mL In the three-necked bottle of stirring, 100mL distilled water is added, adds 3.08g solid NaOH, after stirring and dissolving, is slowly added dropwise at room temperature Carbon disulfide 4.0mL, continues to stir 3h after adding, is then warming up to 65 DEG C, the reaction was continued 30min；It is cooled to room temperature, uses magnet Absorption is separated with solution, then is washed with distilled water 4 times, is placed in vacuum drying chamber in 50 DEG C that drying to constant weight, obtains magnetic retention Chelate adsorption 2.79g.
Embodiment 3
(1) 2.0g average grain diameters are taken to be added to the band of 250mL for the ferroso-ferric oxide microballoon and 80mL absolute ethyl alcohols of 218nm Have in dropping funel, reflux condensing tube and churned mechanically three-necked bottle, it is 95.0% then to add 5.00g mass percentage concentrations Triethylene tetramine, ultrasonic wave Aided Machine stirring 3h.50 DEG C are warming up to, 2.97mL mass percentage concentrations are slowly added dropwise as 99.0% Epoxychloropropane, after being added dropwise to complete, be further continued for reaction 3h, be cooled to room temperature, then with magnet adsorption separate solid matter.
(2) the isolated solid matter of step (1) be transferred to 250mL with dropping funel, reflux condensing tube and In churned mechanically three-necked bottle, 100mL toluene is added, ultrasonic wave Aided Machine stirring 3h, is then slowly dripped by dropping funel The chloroformic solution for adding the mass percentage concentration being configured to by 0.41mL glutaraldehydes to be 10.0%, reacts after dripping at 80 DEG C 3h；Room temperature is cooled to, is separated with magnet adsorption with solvent, ethanol is then used respectively and distills water washing 5 times.
(3) dropping funel, reflux condensing tube and machinery are carried what the solid matter that step (2) obtains was transferred to 250mL In the three-necked bottle of stirring, 90mL distilled water is added, adds 4.10g solid NaOH, after stirring and dissolving, two are slowly added dropwise at room temperature Nitric sulfid 5.3mL, continues to stir 5h after adding, is then warming up to 50 DEG C, the reaction was continued 60min；It is cooled to room temperature, is inhaled with magnet It is attached to be separated with solution, then be washed with distilled water 5 times, it is placed in vacuum drying chamber in 40 DEG C that drying to constant weight, obtains magnetic retention chela Close sorbing material 2.61g.
Embodiment 4
(1) 2.0g average grain diameters are taken to be added to 250mL's for the ferroso-ferric oxide microballoon and 100mL absolute ethyl alcohols of 275nm With in dropping funel, reflux condensing tube and churned mechanically three-necked bottle, it is 95.0% then to add 3.00g mass percentage concentrations Triethylene tetramine, ultrasonic wave Aided Machine stirring 2h.60 DEG C are warming up to, 1.62mL mass percentage concentrations, which are slowly added dropwise, is 99.0% epoxychloropropane, after being added dropwise to complete, is further continued for reaction 2h, is cooled to room temperature, then separate solids with magnet adsorption Matter.
(2) the isolated solid matter of step (1) be transferred to 250mL with dropping funel, reflux condensing tube and In churned mechanically three-necked bottle, 90mL toluene is added, ultrasonic wave Aided Machine stirring 2h, is then slowly added dropwise by dropping funel The chloroformic solution that the mass percentage concentration being configured to by 0.24mL glutaraldehydes is 5.0%, reacts 4h after dripping at 60 DEG C；It is cold But room temperature is arrived, is separated with magnet adsorption with solvent, ethanol is then used respectively and distills water washing 3 times.
(3) dropping funel, reflux condensing tube and machinery are carried what the solid matter that step (2) obtains was transferred to 250mL In the three-necked bottle of stirring, 80mL distilled water is added, adds 1.81g solid NaOH, after stirring and dissolving, two are slowly added dropwise at room temperature Nitric sulfid 2.53mL, continues to stir 3h after adding, is then warming up to 60 DEG C, the reaction was continued 40min；It is cooled to room temperature, uses magnet Absorption is separated with solution, then is washed with distilled water 3 times, is placed in vacuum drying chamber in 50 DEG C that drying to constant weight, obtains magnetic retention Chelate adsorption 2.37g.
Embodiment 5
(1) 2.0g average grain diameters are taken to be added to the band of 250mL for the ferroso-ferric oxide microballoon and 95mL tetrahydrofurans of 435nm Have in dropping funel, reflux condensing tube and churned mechanically three-necked bottle, it is 99.8% then to add 6.00g mass percentage concentrations Tetraethylenepentamine, ultrasonic wave Aided Machine stirring 3h.60 DEG C are warming up to, 2.63mL mass percentage concentrations are slowly added dropwise as 99.0% Epoxychloropropane, after being added dropwise to complete, be further continued for reaction 3h, be cooled to room temperature, then with magnet adsorption separate solid matter.
(2) the isolated solid matter of step (1) be transferred to 250mL with dropping funel, reflux condensing tube and In churned mechanically three-necked bottle, 100mL toluene is added, ultrasonic wave Aided Machine stirs 2.5h, then slow by dropping funel The chloroformic solution that the mass percentage concentration being configured to by 0.42mL glutaraldehydes is 5.0% is added dropwise, is reacted after dripping at 70 DEG C 3.5h；Room temperature is cooled to, is separated with magnet adsorption with solvent, ethanol is then used respectively and distills water washing 5 times.
(3) dropping funel, reflux condensing tube and machinery are carried what the solid matter that step (2) obtains was transferred to 250mL In the three-necked bottle of stirring, 100mL distilled water is added, adds 4.94g solid NaOH, after stirring and dissolving, is slowly added dropwise at room temperature Carbon disulfide 4.51mL, continues to stir 5h after adding, is then warming up to 50 DEG C, the reaction was continued 40min；It is cooled to room temperature, uses magnetic Iron absorption is separated with solution, then is washed with distilled water 5 times, is placed in vacuum drying chamber in 45 DEG C that drying to constant weight, is obtained magnetic solid Body chelate adsorption 2.89g.
Embodiment 6
(1) 2.0g average grain diameters are taken to be added to the band of 250mL for the ferroso-ferric oxide microballoon and 80mL tetrahydrofurans of 435nm Have in dropping funel, reflux condensing tube and churned mechanically three-necked bottle, it is 99.8% then to add 5.00g mass percentage concentrations Tetraethylenepentamine, ultrasonic wave Aided Machine stirring 2.5h.55 DEG C are warming up to, 2.30mL mass percentage concentrations, which are slowly added dropwise, is 99.0% epoxychloropropane, after being added dropwise to complete, is further continued for reaction 2.5h, is cooled to room temperature, then separate solid with magnet adsorption Material.
(2) the isolated solid matter of step (1) be transferred to 250mL with dropping funel, reflux condensing tube and In churned mechanically three-necked bottle, 80mL toluene is added, ultrasonic wave Aided Machine stirring 3h, is then slowly added dropwise by dropping funel The chloroformic solution that the mass percentage concentration being configured to by 0.39mL glutaraldehydes is 5.0%, reacts 3h after dripping at 80 DEG C；It is cold But room temperature is arrived, is separated with magnet adsorption with solvent, ethanol is then used respectively and distills water washing 4 times.
(3) dropping funel, reflux condensing tube and machinery are carried what the solid matter that step (2) obtains was transferred to 250mL In the three-necked bottle of stirring, 80mL distilled water is added, adds 3.80g solid NaOH, after stirring and dissolving, two are slowly added dropwise at room temperature Nitric sulfid 3.4mL, continues to stir 3h after adding, is then warming up to 50 DEG C, the reaction was continued 60min；It is cooled to room temperature, is inhaled with magnet It is attached to be separated with solution, then be washed with distilled water 5 times, it is placed in vacuum drying chamber in 50 DEG C that drying to constant weight, obtains magnetic retention chela Close sorbing material 2.67g.
The process flow diagram of the method for the present invention is as shown in Figure 1, the structure of resulting materials is as shown in Figure 2.To embodiment 1 to 6 resulting materials of embodiment carry out infrared spectrum characterization and transmission electron microscopy, acquired results are basically identical.With the gained of embodiment 1 Material (is denoted as Fe3O4@PM-CS2) exemplified by, infrared spectrum and transmission electron microscope analysis result are as shown in Figure 3 and Figure 4.
Each absworption peak can belong to as follows in Fig. 3 infrared spectrums：Fe3O4Middle 3403.2cm-1For association-the flexible of OH shake Dynamic peak, accordingly in 1628.7cm-1There is the absworption peak of bound water molecule, 1387.5cm-1For the organic matter of preparation process absorption In molecule-CH2- asymmetric stretching vibration peak, 1056.1cm-1For C-O-C in the organic molecule of preparation process absorption Stretching vibration peak, in 628.8,574.9cm-1For Fe3O4The characteristic absorption peak of middle Fe-O.With Fe3O4Compare, when in Fe3O4Table After bread is covered with machine macromolecule link network and chelation group, significant change occurs for infrared spectrum, in 2923.8,2825.7cm-1Place goes out Existing-CH2- symmetrical and asymmetric stretching vibration peak, accordingly in 1349.8cm-1There is its flexural vibrations peak in place； 1447.9cm-1For aminodithioformic acid group (N-CSS—) in C-N stretching vibration absworption peak, 972.4cm-1For- CSS—The stretching vibration peak of middle C=S and C-S；In 1038.2cm-1Weak peak be C-O keys stretching vibration peak；Fe3O4Middle Fe- There occurs a little displacement for the characteristic absorption peak of O.The result shows that successfully by macromolecule link network and chelation group-CSS—Modify Magnetic Fe3O4Microsphere surface.Fig. 4 transmission electron microscope analysis is the result shows that in Fe3O4A thin layer of material is coated, is further proved Succeed macromolecule link network and chelation group-CSS—Modify Fe3O4On microballoon.
Embodiment 7
Using 1~embodiment of embodiment, 6 gained sample as sorbing material, 1 is denoted as respectively#、2#、3#、4#、5#With 6#, match somebody with somebody respectively System contains Cr3+、Zn2+、Cd2+And Pb2+Mass-volume concentration be 100mg/L simulation heavy metal water sample, with unmodified magnetism four Fe 3 O is control sorbing material.Adsorption test condition：(1) adsorption capacity measures, and takes 50mL to simulate heavy metal water sample respectively It is placed in 100mL conical flasks, weighs the sorbing material and magnetic ferroferric oxide of the above-mentioned preparations of 25mg, be placed on constant-temperature table, 2h is vibrated at 25 DEG C, solid particle is separated with solution with magnet adsorption, takes solution in AA100 type Atomic Absorption Spectrometers The concentration of heavy metal ion after measure is adsorbed in (PE companies of the U.S.), calculates the adsorption capacity of sorbing material；(2) adsorption time is surveyed It is fixed, by above-mentioned test method, ion concentration is measured by sampling by time interval of 5min, determines the time for reaching saturation absorption；(3) Heavy metal desorption recycling, makes solid particle be separated with solution adsorption saturation sorbing material, is washed with deionized water with magnet adsorption Wash and slough metal ion not to be adsorbed, be then added in the hydrochloric acid of 0.01mol/L, 1h is vibrated on shaking table, inhaled with magnet It is attached solid particle is separated with solution, then be washed with deionized, the amount of measure elution heavy metal, calculates the recycling of heavy metal Rate, the results are shown in Table 1.
Absorption property of 1 product of the present invention of table to heavy metal ion
As it can be seen from table 1 product of the present invention is to the Cr that dissociates3+、Zn2+、Cd2+And Pb2+Plasma has higher absorption to hold Amount, the rate of adsorption is fast, short up to time of equilibrium adsorption, and the ferroso-ferric oxide that adsorption capacity is far longer than unmodified chelation group is micro- Ball, and there is excellent zeolite regeneration performance.This is because abundant active group is contained on magnetic retention chelate adsorption surface Group, such as dithiocarbonic acid base, amino, imino group and hydroxyl, therefore, substantially increase the chelating adsorption energy to heavy metal ion Power.Further, since product grain core of the present invention is the magnetic ferroso-ferric oxide microballoon of tool, therefore, also with excellent magnetic Separating property, as long as being clarified quickly with attraction, adsorbent solution after absorption, without filtering or centrifuging.
According to above-mentioned test method, consider, in the loss of experiment process sorbing material, 100 times of popularization, i.e., first to take 2.5g sampling tests, progressively reduce experimental scale, and the sorbing material of zeolite regeneration is reused for the absorption of heavy metal ion, with To Pb2+Absorption investigate regeneration and recycle situation, table 2 is recycles the result of 5 times.
The recycling situation of 2 product of the present invention of table is (with to Pb2+Absorption exemplified by)
Table 2 the result shows that, zeolite regeneration influences adsorption capacity very little, and 5 elution cycles are using reaching what saturation was adsorbed Time does not change substantially, though the rate of recovery has been reduced, reduces few.Therefore, magnetic retention of the invention chelating adsorption material Material has the advantages that good heavy metal recovery, regneration of adsorbent material, recycling, service life are longer.
The foregoing is merely the preferred embodiments of the present invention, and according to the above-mentioned design, those skilled in the art are also Can to the process conditions of preparation, various modification can be adapted and conversion, these similar conversion and modification belong to the reality of the present invention Matter.

Claims (8)

1. a kind of magnetic retention chelate adsorption, it is characterised in that it is black solid powder, its structure is in magnetic four oxygen Change the winding of three-iron microsphere surface, coating decoration have the dithiocarbonic acid base that there is strong sequestering power to contents of many kinds of heavy metal ion i.e.- CSS—Macromolecular chain and the cage structure that is formed.
2. the preparation method of the magnetic retention chelate adsorption described in claim 1, it is characterised in that comprise the following steps：
(1) it is 1: 40~50g/ml by ferroso-ferric oxide microballoon by ferroso-ferric oxide microballoon and polar organic solvent mass volume ratio Be added to polar organic solvent in reactor, then by polyethylene polyamine and ferroso-ferric oxide microspheres quality ratio for 1.5~ Add polyethylene polyamine at 3.0: 1, and ultrasonic wave Aided Machine stirs 2~3h, 50~60 DEG C is then warming up to, by epoxychloropropane Epoxychloropropane is slowly added dropwise for 1.0~1.1: 1 with the ratio between the amount of material of polyethylene polyamine, after being added dropwise to complete, is further continued for 2~3h is reacted, is cooled to room temperature, then solid matter is separated with attraction；
(2) step (1) obtained solid material is transferred in reactor, by ferroso-ferric oxide microballoon and the mass volume ratio of toluene Toluene is added for 1: 40~50g/ml, ultrasonic wave Aided Machine stirs 2~3h, then by glutaraldehyde and the thing of polyethylene polyamine The ratio between amount of matter measures glutaraldehyde for 1: 8~10, is configured to the chloroformic solution that mass percentage concentration is 5~10%, is slowly added to Into reactor, 2~4h is crosslinked at 60~80 DEG C；Room temperature is cooled to, is separated with magnet adsorption with solvent, then uses second respectively Alcohol and distillation water washing 3~5 times；
(3) step (2) obtained solid material is transferred in reactor, adds the distillation of 40~50 times of solid matter mass Water, is then 2.2~3.9: 2.0~3.0 by the ratio between amount of material of sodium hydroxide, carbon disulfide and polyethylene polyamine: 1.0, first weigh sodium hydroxide and be added in reactor, measuring carbon disulfide again after to be dissolved is slowly dropped in reactor, adds The reaction was continued 3~5h after complete；Then 50~65 DEG C of 30~60min of reaction are warming up to, are cooled to room temperature, with magnet adsorption and solution Separation, then be washed with distilled water 3~5 times, it is drying to obtain magnetic retention chelate adsorption.
3. the preparation method of magnetic retention chelate adsorption according to claim 2, it is characterised in that magnetism four aoxidizes A diameter of 200-500nm of three-iron microballoon.
4. the preparation method of magnetic retention chelate adsorption according to claim 2, it is characterised in that polarity is organic molten Agent is absolute ethyl alcohol or tetrahydrofuran.
5. the preparation method of magnetic retention chelate adsorption according to claim 2, it is characterised in that polyethylene is more Amine is triethylene tetramine or tetraethylenepentamine.
6. the preparation method of magnetic retention chelate adsorption according to claim 2, it is characterised in that reactor three Neck bottle.
7. the preparation method of magnetic retention chelate adsorption according to claim 2, it is characterised in that drying is vacuum Dry, temperature is 40~50 DEG C.
8. the preparation method of magnetic retention chelate adsorption according to claim 2, it is characterised in that epoxy used Chloropropane, toluene, glutaraldehyde, chloroform, ethanol, sodium hydroxide and carbon disulfide are that analysis is pure.
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