CN105413660B - A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof - Google Patents

A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof Download PDF

Info

Publication number
CN105413660B
CN105413660B CN201510955070.7A CN201510955070A CN105413660B CN 105413660 B CN105413660 B CN 105413660B CN 201510955070 A CN201510955070 A CN 201510955070A CN 105413660 B CN105413660 B CN 105413660B
Authority
CN
China
Prior art keywords
nano
heavy metal
metal ion
meter sio
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510955070.7A
Other languages
Chinese (zh)
Other versions
CN105413660A (en
Inventor
谭业邦
王鑫
荆世尧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to CN201510955070.7A priority Critical patent/CN105413660B/en
Publication of CN105413660A publication Critical patent/CN105413660A/en
Application granted granted Critical
Publication of CN105413660B publication Critical patent/CN105413660B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3071Washing or leaching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3085Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a kind of high absorption heavy metal ion chelating agents based on nanometer titanium dioxide silicon structure and preparation method thereof, it is using nano silicon dioxide nanospheres as base material, by atom transferred free radical living polymerization (ATRP) technology in microsphere surface graft polymers, and then to polymer brush chemical modification, dithiocar-bamate (DTC) functional group with strong absorption chelating ability is introduced in its side chain.The suction-operated site enriched in the bigger serface of such materials combine nanometer silicon dioxide material and polymer side chain structure can realize effective adsorbing separation, such as Cu to contents of many kinds of heavy metal ion within a short period of time2+、Cd2+、Ni2+、Pb2+、Hg2+Deng.The Nano type heavy metal chelant that the present invention reports has huge application potential in improvement heavy metal in water ionic soil field.

Description

A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and its Preparation method
Technical field
The present invention relates to a kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and its preparation sides Method belongs to functional high molecule material synthesis field.
Background technology
Since the mankind are increasingly frequent to industrial activities such as exploitation, the smeltings of heavy metal, damage human survival health Problem of environmental pollution, including heavy metal atmosphere pollution, heavy metal water body pollution, soil pollution by heavy metal etc..Wherein, water pollution There is big, difficult to control, the easy diffusion in region, and serious harm is made to human body by approach such as food chain concentration or drinking-water. Heavy metal ion, which enters human body, to be combined with biological enzyme, and then inhibits protein synthesis, inducible protein denaturation, and disturbs nerve System.The situation is tense for heavy metal water body pollution, becomes one of environmental issue instantly urgently to be resolved hurrily.
In the mask work of heavy metal in water ion, researchers are made that a large amount of trials.Chemiadsorption has Have the advantages that at low cost, capacity is big, easily implement, is recyclable as the important means for administering heavy metal water body pollution, adsorbent and The suction-operated of heavy metal ion generally has both the characteristics of physical absorption and chemisorbed.The research and development of high-performance adsorbent are to improve The key point of heavy metal containing sewage regulation effect.
Chinese patent literature CN103159896A discloses a kind of preparation method of cellulose graft acrylic copolymer, is Using water as solvent, N, N- methylene-bisacrylamides are crosslinking agent, and azodiisobutyronitrile is initiator, using cellulose as matrix, Sodium acrylate and n-vinyl pyrrolidone are comonomer, are copolymerized and are obtained using solution polymerization process.The present invention utilizes height The strong adsorption capacity of the strong sequestering power of molecule chelating agent, carboxyl and amido bond, to the heavy metal ion in waste water and organic sun Ionic dye has the characteristics that adsorption capacity is strong, adsorption capacity is big, percent of decolourization is high, available for the heavy metal in adsorbing and removing waste water The organic cation dyes such as ion and methylene blue.The cellulose copolymer of the present invention reaches the removal rate of Cu in waste water ion 95.1%, 99.5% is reached to the removal rate of methylene blue.But the copolymer specific surface area is small, and adsorption site is few, adsorbing and removing Heavy metal ion ability in waste water is weaker.
The content of the invention
In view of the deficiencies of the prior art, the present invention provide a kind of high absorption heavy metal based on nanometer titanium dioxide silicon structure from Sub- chelating agent and preparation method thereof.
Summary of the invention
The preparation method of high absorption Nano type heavy metal ion chelating agent of the invention, present invention selection compare table with larger The Nano-meter SiO_2 of area2Material is base material, first, is prepared for Nano-meter SiO_22- Br, then, by ATRP, (atom transferred free radical gathers Closing) PGMA is grafted on Nano-meter SiO_2 by living polymerization2- Br surfaces, and then introduce the functional base of a large amount of absorption heavy metal ion Group, finally, Nano type heavy metal ion chelating agent is prepared for by chemical modification.It is chelated and made by the absorption of functional functional group With, can to heavy metal ions in sewage carry out quickly and effectively absorption chelate.Have very in heavy metal-polluted water harnessing field Wide application prospect.
Detailed description of the invention
Technical scheme is as follows:
A kind of high absorption Nano type heavy metal ion chelating agent, has the structure shown in formula (I):
In formula (I), 100≤n≤300.
, according to the invention it is preferred to, heavy metal ion chelating agent specific surface area is 130-170m2/ g, grafting rate 55- 94%.
The preparation method of above-mentioned high absorption Nano type heavy metal ion chelating agent is as follows including step:
(1) Nano-meter SiO_22Surface amino groups be modified
By Nano-meter SiO_22Ultrasound is dispersed in absolute ethyl alcohol, adds 3- aminopropyl triethoxysilane coupling agents (KH550), stir at room temperature, be warming up to 70-90 DEG C, and in N2It flows back, centrifuges in atmosphere, the solids centrifuged is dispersed in It washs in absolute ethyl alcohol, is then dried in vacuo, obtain Nano-meter SiO_22-NH2
(2) Nano-meter SiO_22-NH2Bromo is modified
Nano-meter SiO_2 prepared by step (1)2-NH2Ultrasonic disperse adds in triethylamine, is slowly added dropwise under ice bath in toluene 2- bromine isobutyl acylbromides, react at room temperature, and water and absolute ethyl alcohol washing, vacuum drying obtain Nano-meter SiO_22-Br;
(3) Nano-meter SiO_22The preparation of-PGMA
Nano-meter SiO_2 prepared by above-mentioned steps (2)2- Br is dispersed in glycidyl methacrylate (GMA) and different In the methyl phenyl ethers anisole solution of bromo-butyric acid hydroxyl ethyl ester (HEBIB), liquid nitrogen frozen displacement N2After twice, CuBr is dispersed in system In, freeze-substitution N is carried out again2;By in the methyl phenyl ethers anisole solution addition system of pentamethyl-diethylenetriamine (PMDETA), at room temperature It thaws and is coordinated, then system is warming up to 40-60 DEG C of polymerisation 2-8h;It centrifuges, washs, vacuum drying obtains nanometer SiO2-PGMA;
(4) Nano-meter SiO_22The DTC of-PGMA is modified
By Nano-meter SiO_22- PGMA is scattered in n,N-Dimethylformamide, adds in excessive ethylenediamine (EDA), at room temperature 8-20h is reacted, is centrifuged;Products therefrom is scattered in NaOH aqueous solutions, and CS is added dropwise2, react at room temperature, after centrifugation Washing is dried in vacuo and adsorbs Nano type heavy metal ion chelating agent to get height.
It is currently preferred, in step (1), Nano-meter SiO_22Grain size for 20-600nm, Nano-meter SiO_22Additive amount with The mass ratio of KH550 is 10:1-5:1;The mass ratio of nano silicon dioxide and absolute ethyl alcohol is 1:50-1:100.
It is currently preferred, in step (1), it is warming up to 80-85 DEG C, washing times 2-5 times, vacuum drying temperature 35- 45℃。
It is currently preferred, in step (2), Nano-meter SiO_22-NH2The mass ratio of additive amount and 2- bromine isobutyl acylbromides be 10: 1-5:1, the molar feed ratio of triethylamine and 2- bromine isobutyl acylbromides is 2:1-1:1;Nano-meter SiO_22-NH2It is 1 with toluene mass ratio: 50-1:100。
It is currently preferred, in step (2), reaction time 10-30h, it is preferred that reaction time 24-26h.
Currently preferred, in step (3), the molar ratio of different bromo-butyric acid hydroxyl ethyl ester and glycidyl methacrylate is 1:500-1:200, the molar ratio of glycidyl methacrylate (GMA) and CuBr are 400:1-200:1, pentamethyl divinyl The molar ratio of triamine (PMDETA) and CuBr are 2:1, Nano-meter SiO_22- Br and the mass ratio of glycidyl methacrylate are 1: 2-1:5。
Currently preferred, in step (3), polymeric reaction temperature is 50 DEG C, reaction time 4h, and washing methods is with four Hydrogen furans dispensing laundry is three times.
It is currently preferred, in step (4), Nano-meter SiO_22The mass ratio of-PGMA and ethylenediamine (EDA) is 1:1-1:2, CS2 The molar ratio of dripping quantity and ethylenediamine (EDA) be 1:1;N,N-dimethylformamide and Nano-meter SiO_22The mass ratio of-PGMA is 10:1-5:1, the concentration of NaOH solution is 2mol/L.
Currently preferred, in step (4), the room temperature reaction time is for 24 hours, to wash to wash three with water and methanol successively It is secondary.
The preparation principle of the present invention:
It is described based on Nano-meter SiO_22The high absorption heavy metal ion chelating agent of structure is with Nano-meter SiO_22Material is base material, tool There is the high-specific surface area characteristic of nano material.By ATRP activity polymerizating technologies in Nano-meter SiO_22Material surface situ-formed graft is a large amount of PGMA polymer brush, and then open loop modification is carried out to the epoxy base side chain of PGMA, dithiocarbamates is introduced in its structural unit Formates functional group.Therefore, heavy metal ion chelating agent of the present invention is heavy metal ion adsorbed with what is extremely enriched Active site.
The excellent results of the present invention are as follows:
1st, the present invention is with Nano-meter SiO_22For base material, there is larger specific surface area, heavy metal ion chelating agent specific surface area For 130-170m2/ g, grafting rate 55-94% are conducive to improve the rate of adsorption.
2. the present invention is by atom transfer (ATRRP) activity polymerizating technology, in nanosized SiO_2 surface grafting number of polymers Brush, and abundant active adsorption sites are introduced in its structural unit, structure design is conducive to improve adsorption capacity.
3. the recyclable heavy metal ion of the present invention, and realize the recycling of chelating agent, use cost can be greatly reduced.
4. raw material of the present invention is easy to get, preparation process is simple, and chemical stability is high, and exploitativeness is higher in practical application.
5. the present invention has boundless application prospect in heavy metal-polluted water harnessing field.
Description of the drawings
Fig. 1 is the infrared spectrogram of Nano type heavy metal ion chelating agent prepared by embodiment 1.
Fig. 2 be embodiment 1 prepare Nano type heavy metal ion chelating agent at 25 DEG C to Cu2+、Pb2+、Cd2+Deng a huge sum of money Belong to the curve of adsorption kinetics of ion.
Specific embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
Embodiment 1
A kind of preparation method of high absorption Nano type heavy metal ion chelating agent, step are as follows:
Step (1) Nano-meter SiO_22Surface amino groups be modified
By the Nano-meter SiO_2 of 2g grain sizes 30nm2It is dispersed in 80mL absolute ethyl alcohols, adds in three second of 0.4g 3- aminopropyls Oxysilane coupling agent (KH550), stirs 2h at room temperature, is warming up to 85 DEG C in N2Flow back 1h in atmosphere.It centrifuges, is dispersed in It is washed in absolute ethyl alcohol three times, vacuum drying obtains Nano-meter SiO_22-NH2
Step (2) Nano-meter SiO_22-NH2Bromo is modified
By 1.8g Nano-meter SiO_2s2-NH2Ultrasonic disperse is uniform in 100mL toluene, addition 0.13g triethylamines, under additional ice bath 0.3g 2- bromine isobutyl acylbromides are slowly added dropwise, react 30h at room temperature, second alcohol and water is dried in vacuo after alternately washing twice and is received Rice SiO2-Br。
Step (3) Nano-meter SiO_22The preparation of-PGMA
By 2g Nano-meter SiO_2s2- Br is dispersed in the methyl phenyl ethers anisole solution of 5g GMA and 20mg HEBIB, and liquid nitrogen frozen is put Change N2Afterwards, 15mg CuBr are dispersed in system, carry out freeze-substitution N again2.The methyl phenyl ethers anisole of 18mg PMDETA is molten Liquid injects above-mentioned system, coordination of thawing at room temperature, and then system is warming up to 50 DEG C of polymerization 4h.The SiO that will be obtained2- PGMA is centrifuged Separation, tetrahydrofuran wash three times, vacuum drying.
Step (4) Nano-meter SiO_22The DTC of-PGMA is modified
Nano-meter SiO_2 prepared by 2g2- PGMA is dispersed in n,N-Dimethylformamide, adds in 2g ethylenediamines (EDA), room The lower reaction 12h of temperature, centrifuges.Products therefrom is dispersed in the NaOH aqueous solutions of 2mol/L, and 2.5g CS are added dropwise2, at room temperature instead It should be washed three times to get Nano type metal-chelator with water and ethyl alcohol successively after centrifugation for 24 hours.
Heavy metal ion chelating agent manufactured in the present embodiment is to Cu2+Adsorption capacity be 2.108mmol/g;To Cd2+Suction Attached capacity is 1.077mmol/g;To Pb2+Adsorption capacity be 1.195mmol/g.
It is desorbed after prepared heavy metal ion chelating agent adsorption saturation with the sodium ethylene diamine tetracetate of 0.2mol/L It is attached, then to Cu in the environment of pH=52+、Pb2+、Cd2+Heavy metal ion is adsorbed, to Cu2+Adsorption capacity be 2.056mmol/g;To Cd2+Adsorption capacity be 1.015mmol/g;To Pb2+Adsorption capacity be 1.109mmol/g.The present invention Heavy metal ion chelating agent can realize the recycling recycled and to heavy metal ion, application cost can be greatly reduced.
The adsorption capacity of Nano type heavy metal ion chelating agent measures as follows:Precise certain mass (m) Nano type heavy metal ion chelating agent, add in a series of same volumes (V) various concentration (C0) pH=5 heavy metal ion In solution.It fully adsorbs in constant temperature oscillation shaking table at 25 DEG C, after effect, is separated by filtration.It is sent out with inductance linking atom Penetrate the equilibrium concentration (C that spectrum (ICP-AES) measures heavy metal ion in solutione).Equilibrium adsorption capacities (Qe) count as follows It calculates:
Qe=(C0-Ce)V/m
Embodiment 2
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step (1) grain size of nano silicon dioxide used in is 400nm, and the nano-silica surface grafting rate of preparation is 57.30%.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be 1.593mmol/g;To Cd2+Adsorption capacity be 0.672mmol/g;To Pb2+Adsorption capacity be 0.886mmol/g.
Embodiment 3
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step (2) the room temperature reaction time is 10h in, and prepared nano-silica surface grafting rate is 72.85%.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be 1.775mmol/g;To Cd2+Adsorption capacity be 0.695mmol/g;To Pb2+Adsorption capacity be 0.962mmol/g.
Embodiment 4
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step (3) addition of HEBIB used in is 38mg, and prepared nano-silica surface grafting rate is 75.86%.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be 1.905mmol/g;To Cd2+Adsorption capacity be 0.861mmol/g;To Pb2+Adsorption capacity be 1.037mmol/g.
Embodiment 5
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step (3) addition of CuBr used in and PMDETA is respectively 25mg and 30mg, and prepared nano-silica surface grafting rate is 93.52%.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be 2.351mmol/g;To Cd2+Adsorption capacity be 1.183mmol/g;To Pb2+Adsorption capacity be 1.336mmol/g.
Embodiment 6
The preparation method of high absorption Nano type heavy metal ion chelating agent as described in Example 1, except that step (4) EDA used in and Nano-meter SiO_22The mass ratio of-PGMA is 2:1, CS used2Molar ratio with EDA is 1:1.
Heavy metal ion chelating agent manufactured in the present embodiment is in the environment of pH=5 to Cu2+Adsorption capacity be 2.253mmol/g;To Cd2+Adsorption capacity be 1.160mmol/g;To Pb2+Adsorption capacity be 1.258mmol/g.

Claims (7)

1. a kind of preparation method of high absorption Nano type heavy metal ion chelating agent, as follows including step:
(1) Nano-meter SiO_22Surface amino groups be modified
By Nano-meter SiO_22Ultrasound is dispersed in absolute ethyl alcohol, adds 3- aminopropyl triethoxysilane coupling agent KH550, room temperature Lower stirring, is warming up to 70-90 DEG C, and in N2It flows back, centrifuges, the solids centrifuged, which is dispersed in absolute ethyl alcohol, to be washed in atmosphere It washs, is then dried in vacuo, obtain Nano-meter SiO_22-NH2
(2) Nano-meter SiO_22-NH2Bromo is modified
By step(1)The Nano-meter SiO_2 of preparation2-NH2Ultrasonic disperse adds in triethylamine, 2- bromines is slowly added dropwise under ice bath in toluene Isobutyl acylbromide, reacts at room temperature, and water and absolute ethyl alcohol washing, vacuum drying obtain Nano-meter SiO_22-Br;
(3) Nano-meter SiO_22The preparation of-PGMA
By above-mentioned steps(2)The Nano-meter SiO_2 of preparation2- Br is dispersed in glycidyl methacrylate GMA and different bromo-butyric acid In the methyl phenyl ethers anisole solution of hydroxyl ethyl ester, liquid nitrogen frozen displacement N2After twice, CuBr is dispersed in system, is freezed again Replace N2;By coordination of in the methyl phenyl ethers anisole solution addition system of pentamethyl-diethylenetriamine PMDETA, thawing at room temperature, Ran Houti System is warming up to 40-60 DEG C of polymerisation 2-8 h;It centrifuges, washs, vacuum drying obtains Nano-meter SiO_22-PGMA;Different bromine fourth The molar ratio of sour hydroxyl ethyl ester and glycidyl methacrylate is 1:500-1:200, glycidyl methacrylate GMA Molar ratio with CuBr is 400:1-200:1, the molar ratio of pentamethyl-diethylenetriamine PMDETA and CuBr are 2:1, nanometer SiO2- Br and the mass ratio of glycidyl methacrylate are 1:2-1:5;
(4) Nano-meter SiO_22The DTC of-PGMA is modified
By Nano-meter SiO_22- PGMA is scattered in n,N-Dimethylformamide, is added in excessive ethylenediamine EDA, is reacted 8- at room temperature 20 h are centrifuged;Products therefrom is scattered in NaOH aqueous solutions, and CS is added dropwise2, react at room temperature, after centrifugation successively It is washed three times with water and methanol, is dried in vacuo and adsorbs Nano type heavy metal ion chelating agent to get height;Nano-meter SiO_22- PGMA with The mass ratio of ethylenediamine EDA is 1:1-1:2, CS2The molar ratio of dripping quantity and ethylenediamine EDA be 1:1;N, N- dimethyl Formamide and Nano-meter SiO_22The mass ratio of-PGMA is 10:1-5:1, the concentration of NaOH solution is 2 mol/L, reacts at room temperature the time For 24 h.
2. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step Suddenly(1)In, Nano-meter SiO_22Grain size for 20-600 nm, Nano-meter SiO_22Additive amount and KH550 mass ratio be 10:1-5:1;It receives Rice SiO2Mass ratio with absolute ethyl alcohol is 1:50-1:100.
3. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step Suddenly(1)In, 80-85 DEG C is warming up to, washing times 2-5 times, vacuum drying temperature is 35-45 DEG C.
4. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step Suddenly(2)In, Nano-meter SiO_22-NH2The mass ratio of additive amount and 2- bromine isobutyl acylbromides be 10:1-5:1, triethylamine and 2- bromine isobutyls The molar feed ratio of acylbromide is 2:1-1:1;Nano-meter SiO_22-NH2It is 1 with toluene mass ratio:50-1:100.
5. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step Suddenly(2)In, the reaction time is 10-30 h.
6. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that step Suddenly(3)In, polymeric reaction temperature be 50 DEG C, the reaction time be 4 h, washing methods be with tetrahydrofuran dispensing laundry three times.
7. the preparation method of high absorption Nano type heavy metal ion chelating agent according to claim 1, which is characterized in that weight Metal ion chelation agent specific surface area is 130-170 m2/ g, grafting rate 55-94%.
CN201510955070.7A 2015-12-17 2015-12-17 A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof Active CN105413660B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510955070.7A CN105413660B (en) 2015-12-17 2015-12-17 A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510955070.7A CN105413660B (en) 2015-12-17 2015-12-17 A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105413660A CN105413660A (en) 2016-03-23
CN105413660B true CN105413660B (en) 2018-05-22

Family

ID=55492462

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510955070.7A Active CN105413660B (en) 2015-12-17 2015-12-17 A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105413660B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105921083B (en) * 2016-06-07 2019-06-11 东华大学 The preparation method and its product of graded composite aeroge based on three-dimensional network shape
CN106395965B (en) * 2016-10-10 2019-06-18 天津工业大学 A method of rich in thioamido functional magnetic material efficient absorption heavy metal
CN106745457B (en) * 2016-12-26 2019-12-17 深圳大学 Hollow fiber membrane for selectively adsorbing gold ions and preparation method and application thereof
CN108264925B (en) * 2017-12-25 2020-08-18 华东理工大学 Non-acidic crude oil demetallizing agent with core-shell structure and preparation method and application thereof
CN109647353B (en) * 2019-01-30 2022-01-04 常州市新未来化工有限公司 Heavy metal sewage composite treating agent and preparation method and application thereof
CN112642409B (en) * 2020-03-18 2022-08-09 中国科学院过程工程研究所 Cleaning material and preparation method and application thereof
CN111704907B (en) * 2020-06-15 2021-07-16 河南大学 Heavy metal passivator and preparation method and application thereof
CN114058153B (en) * 2020-12-21 2022-09-13 中国科学院兰州化学物理研究所 SiO (silicon dioxide) 2 -PGMA reinforced epoxy resin composite material and preparation method thereof
CN112897671A (en) * 2021-01-19 2021-06-04 西南科技大学 Heavy metal ion capturing material and preparation method thereof
CN113087216A (en) * 2021-04-24 2021-07-09 中城园林工程有限公司 Garden sewage treatment process
CN114132960B (en) * 2021-12-21 2022-09-23 湖北亚星电子材料有限公司 Preparation method for purifying titanium dioxide by composite solid phase column

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60158203A (en) * 1984-01-30 1985-08-19 Daicel Chem Ind Ltd Resolving agent
CN101402033A (en) * 2008-10-30 2009-04-08 上海大学 Chelate adsorption material and method of producing the same
CN101824273A (en) * 2010-03-31 2010-09-08 中科院广州化学有限公司 Fluoropolymer/inorganic nano-hybrid particle modified ultraviolet photocured paint and preparation method thereof
CN102060995A (en) * 2010-11-19 2011-05-18 中南大学 Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60158203A (en) * 1984-01-30 1985-08-19 Daicel Chem Ind Ltd Resolving agent
CN101402033A (en) * 2008-10-30 2009-04-08 上海大学 Chelate adsorption material and method of producing the same
CN101824273A (en) * 2010-03-31 2010-09-08 中科院广州化学有限公司 Fluoropolymer/inorganic nano-hybrid particle modified ultraviolet photocured paint and preparation method thereof
CN102060995A (en) * 2010-11-19 2011-05-18 中南大学 Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ATRP法在纳米硅胶粒子表面接枝聚甲基丙烯酸缩水甘油酯;何三雄等;《高分子材料科学与工程》;20070531;第23卷(第3期);第100页右栏第1段-第103页右栏第2段 *
Synthesis and adsorption performance of dithiocarbamate-modifiedglycidyl methacrylate starch;Xiumei Cheng等;《Carbohydrate Polymers》;20130410;第96卷;第320页右栏第2段-第321页右栏第1段,第324页"4.Conclusions" *
乙二胺多(二硫代甲酸钠)的合成及对含铜废水的去除性能;刘立华等;《湖南科技大学学报(自然科学版)》;20120630;第27卷(第2期);第96页左栏第1段-第99页左栏第5段 *
原子转移自由基聚合制备PDMAEMA亲水作用色谱固定相及其性能评价;杨静等;《化学学报》;20120831;第70卷(第16期);第1725页摘要,第1726页左栏第2段-第1727页左栏第2段,第1730页"4 实验部分" *

Also Published As

Publication number Publication date
CN105413660A (en) 2016-03-23

Similar Documents

Publication Publication Date Title
CN105413660B (en) A kind of high absorption heavy metal ion chelating agent based on nanometer titanium dioxide silicon structure and preparation method thereof
CN106799215B (en) A kind of porous spherical crosslinked resin-graphene oxide composite adsorption material and its preparation and application
CN102977256B (en) Acrylic ester-attapulgite composite oil-absorbing material and preparation method thereof
CN107082894B (en) A kind of double-network hydrogel adsorbent and preparation method thereof and application as heavy metal absorbent
CN107983300A (en) Biological carbon composite of manganese dioxide modification and its preparation method and application
CN104841293B (en) Oil water separation nanofiber membrane with CO2 stimulus response as well as preparation method and application thereof
CN107866209B (en) Highly selective magnetic dye sorbent of one kind and preparation method thereof
CN105498707A (en) Preparation method and application of modified graphene oxide/chitosan composite material
CN107552007B (en) Ion liquid modified magnalium laminar double-hydroxide adsorbent and its preparation and application
CN102153693A (en) Salt-tolerant acrylic absorbent resin and method for preparing same
CN109174023A (en) A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application
CN107303483A (en) Multiple organic decoration magnetic composite and preparation method thereof and application in the treatment of waste water
CN111889077A (en) Preparation of modified magnetic zeolite imidazole framework material and adsorption of trace amount of ceftazidime in water
CN109704432B (en) One-pot method for preparing UIO-66-NH2Method for preparing functional monomer composite material and application of functional monomer composite material in adsorption of antibiotics
CN102633943A (en) Preparation method of starch super-absorbent resin
CN107583624A (en) A kind of graphene oxide/sodium alginate composite microsphere and its preparation method and application
CN102872790A (en) Sulfate radical sorbent magnetic nanometer zirconium hydroxide and preparation method thereof
CN107081123A (en) Magnetic magnesium hydroxide adsorbent and preparation method thereof
CN109608655A (en) A kind of bifunctional group MOFs material and the preparation method and application thereof
CN107556435A (en) A kind of preparation method and application of PAMC grafting carboxymethyl cellulose
CN106496418A (en) A kind of chitosan magnetic lead ion imprinted polymer and preparation method thereof
CN105771912B (en) A kind of multifunctional bio adsorbent material and preparation method thereof
CN104017144A (en) Nanocomposite and preparation method thereof
CN102659977B (en) Method for preparing columnar three-dimensional ordered macroporous chelating resin
CN104927063A (en) Method for adsorbing and recycling phenolic compounds in industrial wastewater and method for manufacturing adsorption materials

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant