CN109046275A - It is a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead - Google Patents

It is a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead Download PDF

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CN109046275A
CN109046275A CN201810733407.3A CN201810733407A CN109046275A CN 109046275 A CN109046275 A CN 109046275A CN 201810733407 A CN201810733407 A CN 201810733407A CN 109046275 A CN109046275 A CN 109046275A
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deionized water
added
stirring
sio
particle
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陈国�
季久江
赵珺
陈宏文
郭洪伟
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Xiamen Pruimeger Biotechnology Co Ltd
Huaqiao University
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Xiamen Pruimeger Biotechnology Co Ltd
Huaqiao University
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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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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 invention discloses a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead, with Fe3O4Upper amino and mercapto groups are modified for carrier, after packet silicon.Resulting magnetic nano-particle is prepared to the removal rate height of lead using the method for the present invention, and adsorption capacity is big, and recycling effect is good and eluting agent is few, and elution effect is good.

Description

It is a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead
Technical field
The present invention relates to the dirty water decontamination handles fields more particularly to a kind of for removing the magnetic nano-particle of heavy metal lead Preparation method.
Background technique
Heavy metal in waste water is mainly derived from mining industry, intermetallic composite coating, process hides, pharmaceuticals, pesticide, organic chemical, rubber The industries such as glue, plastics and timber processing.The heavy metal pollution of water body has very strong diffusivity and difficult to control, due to it There is cumulative bad in vivo, once into that will add up in human body in animal and plant body, finally to the biosystem of people and Psychiatric system plays the role of destructive.The harm of heavy metal is it is well known that the Minamata occurred in Japan for example reported in the early time Sick (mercury poisoning) and Itai-itai diseases (cadmium poisoning) are all and China Anhui Huaining, Zhejiang moral in recent years as caused by heavy metal pollution Clearly, there is the blood lead event of lead poisoning in succession in the ground such as Guangdong Zijin.Heavy metal pollution event emerges one after another, and is never interrupted.Such as The present, heavy metal pollution oneself become China's water pollution High risk population.It is urgent to find a kind of method for effectively removing heavy metal In the eyebrows and eyelashes.
The common method for removing removing heavy metals has: ion-exchange, solvent extraction, chemical precipitation method, biological restoration, anti- Osmosis and absorption method etc..For absorption method since its is easy to operate, processing quickly, becomes one of common method of removing heavy metals. But there are at high cost, low to some heavy metal removing rates, adsorbance is small, is also easy to produce secondary pollution problems for existing adsorbent. Therefore, cost, the removal of heavy metal ions rate for improving adsorbent how are reduced, increases adsorbance and reduces and caused in use process Secondary pollution problem be current research hotspot.
In consideration of it, the present inventor furthers investigate the above problem, there is this case generation then.
Summary of the invention
In view of the deficiencies in the prior art, the purpose of the present invention is to provide a kind of for adsorbing the magnetic Nano of heavy metal lead The preparation method of particle, this method prepare resulting magnetic nano-particle to the removal rate height of lead, and adsorption capacity is big, recycles Effect is good and eluting agent is few, and elution effect is good.
To achieve the goals above, the present invention adopts the following technical scheme:
It is a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead, with Fe3O4For carrier, modified after packet silicon Upper amino and mercapto groups, it is specific the preparation method is as follows:
(1) four water irons of Iron(III) chloride hexahydrate and 2.0-2.5g that gross mass is 3.5-4.5g are dissolved in In 60-100ml deionized water, it is stirring evenly and then adding into 7-9ml concentrated ammonia liquor, 0.2-0.5g nonyl two is added when reacting 1-3min Acid, is formed by mixed liquor and is heated to 65-75 DEG C and be stirred to react 0.8-1.2h, the method that resulting precipitating uses Magnetic Isolation It is separated, and resulting magnetic sediment ethyl alcohol and deionized water is washed obtain Fe several times respectively3O4；
(2) Fe that will be obtained3O4It takes 0.5-1g to be added in 400-600ml dehydrated alcohol, is stirring evenly and then adding into 10-20ml Concentration is the ammonium hydroxide of 24%-25%, takes 0.5-1.5ml tetraethyl orthosilicate to be at the uniform velocity added dropwise in mixed solution and carries out particle surface Packet silicon, 10-12h are added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is added in 50-100ml toluene, is stirring evenly and then adding into the 3- chlorine of 0.2-0.6ml The PEI of propyl trimethoxy silicane and 0.2-0.6ml, return stirring 11-13h progress surface is modified at 75-85 DEG C, uses ethyl alcohol It is washed respectively with deionized water and obtains Fe several times3O4@SiO2-PEI；
(4) by resulting Fe3O4@SiO270-150ml acetone is added in-PEI, and 6-12ml epoxychloropropane room temperature is first added Return stirring 10-13h adds 2-6g thiocarbamide and stirs 10-13h under alkaline condition, washed respectively with ethyl alcohol and deionized water Final product Fe is obtained several times3O4@SiO2-PEI-SH。
Iron(III) chloride hexahydrate 3.5-4.5g is first weighed in the step (1) to be dissolved in the deionized water of 71.25ml, is formed The liquor ferri trichloridi is heated with stirring to 70 DEG C by liquor ferri trichloridi, and it is molten to weigh four hydration iron 2.0-2.5g In 5ml deionized water, iron solution is obtained, after filtering, takes iron solution described in 3.75ml that the trichlorine is added Change in ferrous solution, under intense agitation, 7-9ml concentrated ammonia liquor is added, the azelaic acid of 0.2-0.5g is added after reacting 1min, and Continue to be vigorously stirred 1h at 70 DEG C, be washed respectively for several times by black precipitate Magnetic Isolation and with ethyl alcohol and deionized water；
The dosage difference of Iron(III) chloride hexahydrate, four hydration irons, concentrated ammonia liquor and azelaic acid in the step (1) For 4.05g, 2.2g, 9ml, 0.5g, the stirring rate after azelaic acid is added is 250~350r/min.
In the step (2), at room temperature, the Fe that will be obtained3O4It takes 0.5g to be added in 500ml dehydrated alcohol, stirs evenly The ammonium hydroxide that 20ml concentration is 24%-25% is added afterwards, takes 1ml tetraethyl orthosilicate to be at the uniform velocity added dropwise in mixed solution and carries out particle Surface packet silicon, tetraethyl orthosilicate 12h are added dropwise, and are stirred, stir to mixed liquor while tetraethyl orthosilicate is added dropwise Mixing rate is 250~350 r/min, is washed with ethyl alcohol and deionized water respectively obtain Fe several times after the reaction was completed3O4@SiO2。
The Fe that will be obtained in the step (3)3O4@SiO2It takes 0.5g to be added in 60ml toluene, is stirring evenly and then adding into The 3- r-chloropropyl trimethoxyl silane of 0.3ml and the PEI of 0.5ml, return stirring 12h progress surface is modified at 80 DEG C, stirring Rate is 250~350r/min, is washed respectively with ethyl alcohol and deionized water and obtains Fe several times3O4@SiO2-PEI。
By resulting Fe in the step (4)3O4@SiO2- PEI takes 0.5g that 100ml acetone is added, and 10ml epoxy is first added Chloropropane, in room temperature return stirring 12h, the NaOH solution being then added, so that mixed liquor adds 5g thiocarbamide in room in alkalinity The lower return stirring 12h of temperature, stirring rate is 250~350r/min, is washed and is obtained several times most respectively with ethyl alcohol and deionized water Final product Fe3O4@SiO2-PEI-SH。
The concentration of step (4) NaOH solution is 5mol/L, additional amount 4ml.
After technical solution of the present invention, Fe is prepared with coprecipitation in step (1)3O4Particle simple process, raw material six Iron chloride hexahydrate, four hydration irons and ammonium hydroxide source are wide, are easily enlarged production, and make Fe by azelaic acid3O4Grain Sublist face introduces a large amount of carboxyls, generates electrostatic repulsion, improves Fe by electrostatic repulsion3O4Particle dispersing characteristic, reduces Fe3O4 The coagulation of particle, Fe3O4The dispersion degree of particle is greatly improved, and increases Fe3O4The total surface area of particle, for it is subsequent Fe3O4Particle surface carries out modification and provides good basis；Magnetic Nano Fe simultaneously3O4Inherently has preferable superparamagnetic Property, with magnetic Nano Fe3O4Particle is the adsorbent of shell preparation, can quickly be recycled using its superparamagnetism under magnetic field condition The adsorbent.Tetraethyl orthosilicate divides 10-12h to be at the uniform velocity added dropwise to progress particle surface packet silicon in mixed solution in step (2), So that tetraethyl orthosilicate is fully hydrolyzed, in Fe3O4Surface coats upper SiO2Silicon layer, SiO2It is wrapped in Fe3O4Outer formation is core Shell structure, thus SiO2It is wrapped to form steric hindrance, reduces reunion, overcomes and is introduced directly into positive silicic acid tetrem in alcohol-water system The ester cladding silicon layer problem that causes particle easy to reunite, thus can will be coated in reaction system silicon layer particle concentration from 1g/L Be increased to 10g/L or more, thus reach magnanimity prepare monodisperse, high-intensity magnetic field responsiveness core-shell structure silicon substrate magnetic Nano The purpose of grain；Dehydrated alcohol is used simultaneously, reduces the content of water in mixed liquor, so that tetraethyl orthosilicate hydrolysis rate is controllable Property increase, the silicon layer of cladding is more uniform and then keeps its dispersibility more preferable.Step (3) and step (4) introduce-NH simultaneously2With- SH group, due to-NH2There is fabulous compatibility to heavy metal lead with-SH group, therefore the absorption for increasing adsorbent is held Amount.
Therefore, this method prepares resulting magnetic nano-particle to the removal rate height of lead, and adsorption capacity is big, recycles effect Fruit is good and eluting agent is few, and elution effect is good.
Specific embodiment
The present invention is described further combined with specific embodiments below.
Embodiment one
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.2g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 82mg.
Embodiment two
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 113mg.
Embodiment three
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 10ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 76mg.
Example IV
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 0.5ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 110mg.
Embodiment five
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1.5ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 84mg.
Embodiment six
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.2ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 96mg.
Embodiment seven
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.6ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 93mg.
Embodiment eight
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.2ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 99mg.
Embodiment nine
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.6ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 103mg.
Embodiment ten
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 6ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 66mg.
Embodiment 11
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 12ml room temperature return stirring 12h, is added thiocarbamide 5g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 110mg.
Embodiment 12
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 2g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 113mg.
Embodiment 13
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 6g, and 4ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 108mg.
Embodiment 14
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 2ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 95mg.
Embodiment 15
(1) it weighs Iron(III) chloride hexahydrate 4.05g and is dissolved in 71.25ml deionized water, with 300r/min in three-necked flask Rate stirring, and be heated to 70 DEG C, weigh four hydration iron 2.2g and be dissolved in 5ml deionized water, filter, take Three-necked flask is added in 3.75ml, rapidly joins 9ml concentrated ammonia liquor, the addition azelaic acid 0.5g after reacting 1min, after continuation of insurance at 70 DEG C The rate for holding 300r/min continues to wash respectively 3 times after stirring 1h by black precipitate Magnetic Isolation, and with ethyl alcohol and deionized water, Obtain Fe3O4；
(2) by the resulting Fe3O40.5g is taken to be dissolved in 500ml dehydrated alcohol, being stirring evenly and then adding into concentration is 25% Ammonium hydroxide 20ml is then vigorously stirred with the rate of 300r/min, and 1ml tetraethyl orthosilicate is slowly added dropwise and carries out particle surface packet Silicon, the tetraethyl orthosilicate divide 12h to be added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe for several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is dissolved in 60ml toluene, chloropropyl front three is stirring evenly and then adding into three-necked flask Oxysilane 0.3ml, PEI 0.5ml, 80 DEG C of return stirring 12h carry out that surfaces are modified by black precipitate Magnetic Isolation and to use second Pure and mild deionized water is washed respectively obtains Fe for several times3O4@SiO2-PEI；
(4) by the Fe after washing3O4@SiO2- PEI is dissolved in 100ml acetone, and ring is stirring evenly and then adding into three-necked flask Oxygen chloropropane 10ml room temperature return stirring 12h, is added thiocarbamide 5g, and 6ml NaOH (5mol/L) continues black precipitate to stir after 1h Magnetic Isolation ethyl alcohol and deionized water are washed respectively obtains final product for several times.
(5) by the Pb of above-mentioned particle 1g and 1L2+Solution (200mg/L) mixing, stirring at normal temperature 10min, every gram of magnetic Nano Pb is adsorbed in particle absorption agent2+Up to 88mg.
As the measurement of the absorption property to adsorbent made from embodiment 1-15, measurement result is as shown in the table.
By upper table, it can be seen that, using embodiment 2 or embodiment 12, resulting adsorbent effect is best.
Heretofore described PEI is polyethyleneimine.
The product form and style of the embodiment and non-limiting the invention patent, the common skill of any technical field The appropriate changes or modifications that art personnel do it all should be regarded as the patent category for not departing from the invention patent.

Claims (7)

1. a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead, it is characterised in that: with Fe3O4For carrier, packet Upper amino and mercapto groups are modified after silicon, the preparation method is as follows:
(1) four water irons of Iron(III) chloride hexahydrate and 2.0-2.5g that gross mass is 3.5-4.5g are dissolved in 60- In 100ml deionized water, it is stirring evenly and then adding into 7-9ml concentrated ammonia liquor, 0.2-0.5g azelaic acid, institute are added when reacting 1-3min The mixed liquor of formation is heated to 65-75 DEG C and is stirred to react 0.8-1.2h, and resulting precipitating is divided using the method for Magnetic Isolation From resulting magnetic sediment ethyl alcohol and deionized water are washed several times respectively then, obtain Fe3O4；
(2) Fe that will be obtained3O4It takes 0.5-1g to be added in 400-600ml dehydrated alcohol, is stirring evenly and then adding into 10-20ml concentration For the ammonium hydroxide of 24%-25%, 0.5-1.5ml tetraethyl orthosilicate is taken at the uniform velocity to be added dropwise to progress particle surface packet in mixed solution Silicon, 10-12h are added dropwise, and are washed respectively with ethyl alcohol and deionized water and obtain Fe several times3O4@SiO2；
(3) Fe that will be obtained3O4@SiO2It is added in 50-100ml toluene, is stirring evenly and then adding into the 3- chloropropyl of 0.2-0.6ml The PEI of trimethoxy silane and 0.2-0.6ml, return stirring 11-13h progress surface is modified at 75-85 DEG C, with ethyl alcohol and goes Ionized water washs obtain Fe several times respectively3O4@SiO2-PEI；
(4) by resulting Fe3O4@SiO270-150ml acetone is added in-PEI, and the reflux of 6-12ml epoxychloropropane room temperature is first added and stirs 10-13h is mixed, 2-6g thiocarbamide is added and stirs 10-13h under alkaline condition, washed respectively several times with ethyl alcohol and deionized water Obtain final product Fe3O4@SiO2-PEI-SH。
2. a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead as described in claim 1, it is characterised in that: Iron(III) chloride hexahydrate 3.5-4.5g is first weighed in step (1) to be dissolved in the deionized water of 71.25ml, and it is molten to form ferric trichloride The liquor ferri trichloridi is vigorously stirred by liquid, and is heated to 70 DEG C, is weighed four hydration iron 2.0-2.5g and is dissolved in 5ml deionized water obtains iron solution, after filtering, takes iron solution described in 3.75ml that the tri-chlorination is added In ferrous solution, under intense agitation, 7-9ml concentrated ammonia liquor is added, the azelaic acid of 0.2-0.5g is added after reacting 1min, and Continue to be vigorously stirred 1h at 70 DEG C, precipitated magnetic is separated and is washed respectively for several times with ethyl alcohol and deionized water.
3. a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead as claimed in claim 2, it is characterised in that: Iron(III) chloride hexahydrate in the step (1), four hydration irons, concentrated ammonia liquor and azelaic acid dosage be respectively 4.05g, 2.2g, 9ml, 0.5g, the rate being vigorously stirred are 250~350r/min.
4. a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead as described in claim 1, it is characterised in that: In the step (2), at room temperature, the Fe that will be obtained3O4It takes 0.5g to be added in 500ml dehydrated alcohol, is stirring evenly and then adding into 20ml concentration is the ammonium hydroxide of 24%-25%, and 1ml tetraethyl orthosilicate is taken at the uniform velocity to be added dropwise to progress particle surface packet in mixed solution Silicon, tetraethyl orthosilicate 12h are added dropwise, and are stirred while tetraethyl orthosilicate is added dropwise to mixed liquor, stirring rate For 250~350r/min, is washed respectively with ethyl alcohol and deionized water obtain Fe several times after the reaction was completed3O4@SiO2。
5. a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead as described in claim 1, it is characterised in that: The Fe that will be obtained in the step (3)3O4@SiO2It takes 0.5g to be added in 60ml toluene, is stirring evenly and then adding into the 3- chlorine of 0.3ml The PEI of propyl trimethoxy silicane and 0.5ml, it is modified to carry out surface by return stirring 12h at 80 DEG C, and stirring rate is 250~ 350r/min is washed respectively with ethyl alcohol and deionized water and is obtained Fe several times3O4@SiO2-PEI。
6. a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead as described in claim 1, it is characterised in that: By resulting Fe in the step (4)3O4@SiO2- PEI takes 0.5g that 100ml acetone is added, and 10ml epoxychloropropane is first added, 2-6mlNaOH solution is then added in room temperature return stirring 12h, so that mixed liquor adds 5g thiocarbamide and return at room temperature in alkalinity Stream stirring 12h, stirring rate is 250~350r/min, is washed respectively with ethyl alcohol and deionized water and obtains final product several times Fe3O4@SiO2-PEI-SH。
7. a kind of for removing the preparation method of the magnetic nano-particle of heavy metal lead as claimed in claim 6, it is characterised in that: The concentration of the NaOH solution is 5mol/L, additional amount 4ml.
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Application publication date: 20181221