CN109052542A - A kind of preparation method for the modified carbon nano-tube removing mercury ions in waste water - Google Patents

A kind of preparation method for the modified carbon nano-tube removing mercury ions in waste water Download PDF

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Publication number
CN109052542A
CN109052542A CN201811037520.4A CN201811037520A CN109052542A CN 109052542 A CN109052542 A CN 109052542A CN 201811037520 A CN201811037520 A CN 201811037520A CN 109052542 A CN109052542 A CN 109052542A
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China
Prior art keywords
tube
carbon nano
waste water
preparation
mercury ions
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CN201811037520.4A
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Chinese (zh)
Inventor
舒黎幼
邵明
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Sharp Bio Tech Ltd Suzhou One Hundred
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Sharp Bio Tech Ltd Suzhou One Hundred
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Priority to CN201811037520.4A priority Critical patent/CN109052542A/en
Publication of CN109052542A publication Critical patent/CN109052542A/en
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    • 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
    • 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
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • 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
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/262Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • 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
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The present invention relates to a kind of preparation methods that the poly-dopamine for removing mercury ions in waste water is carbon nano-tube modified, and step includes: the pretreatment of (1) modified carbon nano-tube;(2) preparation of poly-dopamine modified lithium carbon nanotube;(3) mercury ion is adsorbed from waste water using modified carbon nano-tube;(4) adsorbance of test absorption front and back mercury ion, evaluates the absorption property of modified carbon nano-tube.This method is simple, efficient, suitable for quickly removing the metal mercury ions waste water.

Description

A kind of preparation method for the modified carbon nano-tube removing mercury ions in waste water
Technical field
The invention belongs to the application fields of Environmental Chemistry, the in particular to minimizing technology of heavy metal ions in wastewater.
Background technique
With the rapid development of industry, heavy metal ion pollution has seriously affected human society survival and development and has formed For the hot issue of World Focusing.Mercury ion in environment is easy to enter in human body by food chain, can make to human health At serious threat, it can cause to have a headache, have difficulty in breathing, cause intravascular hemolysis, injuring nerve system, based on these harm, people Have studied a variety of methods to administer mercury ion waste liquid.Oneself is had investigated various ways to remove mercury ion to people, Such as the filtering of the precipitation method, film, ion exchange, electrolysis method and absorption method, wherein absorption method is the most common method of people, this Method operation is terse, and energy consumption is few, and expense is low, it is most important that removal rate is high.Nano material in adsorbent material has many suctions Attached advantage, therefore by favor.
Carbon nanotube possesses in the bigger serface and high stability that traditional material does not have in terms of noxious substance Blank pipe shape special construction makes it possess huge applications value in wastewater treatment and other field, especially in absorption heavy metal side Face is had outstanding performance, while being studied also more.In order to preferably adsorb, be enriched with to heavy metal ion, researcher utilizes carbon The characteristic that nanotube surface is easily modified is modified processing to it, its surface is made to connect upper specific functional group, can be to certain Heavy metal has a good absorption property, this kind of application studies be paid more and more attention and carried out a variety of modification groups or The research of polymer for heavy metals absorption.
Dopamine is that can be occurred under aerobic weak basic condition based on it with good adhesiveness to the modification of material Autoxidation polymerization, generates a kind of one poly-dopamine of macromolecule and is adhered to matrix surface.This kind of macromolecule equally has various active Group has good adsorptivity to positive heavy metal ion.It is basic adsorbent material with carbon nanotube, with chemical means to it Surface modified, developing the high heavy-metal adsorption material of the novel adsorbance of one kind has potential application prospect.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of method for removing heavy metal in waste water mercury ion, this method The carbon nanotube modified using dopamine is as adsorbent, time-consuming less using the method for Static Adsorption, being capable of quick, high dose Slave waste water in adsorb metal mercury ions;The prices of raw materials used in the present invention are cheap, obtained modified carbon nano-tube Surface area with higher, adsorption capacity is strong, the potentiality with subsequent related application.
A kind of preparation method of the modified carbon nano-tube of removal mercury ions in waste water of the invention, comprising:
(1) pretreatment of carbon nanotube: take appropriate unmodified carbon nanotube in crucible, being placed in one timing of heating in Muffle furnace Between, agraphitic carbon impurity is removed, cooling, kept dry is spare;
(2) poly-dopamine modified lithium carbon nanotube: weighing the carbon nanotube in step (1), ultrasonic treatment, then weighs a certain amount of more Bar amine hydrochlorate, is placed in Tris-HCl buffer, room temperature magnetic agitation certain time, is repeatedly washed through ultrapure water to neutrality, The modified carbon nano-tube washed is dried into 8 ~ 12 h in a vacuum drying oven, it is spare.
The temperature of the Muffle furnace as described in step (1) is 300 ~ 400 DEG C.
The heating time as described in step (1) is 20 ~ 50 min.
The quality of carbon nanotube described in the step (2) is 1.0 ~ 3.0 g.
The time of the ultrasonic treatment of carbon described in the step (2) is 20 ~ 50 min.
The quality of carbon dopamine hydrochloride described in the step (2) is 0.5 ~ 2.0 g.
The concentration of Tris-HCl buffer described in the step (2) are as follows: 0.001 ~ 0.1 mol/L, pH value are 6 ~ 9.
The time being stirred at room temperature described in the step (2) are as follows: 10 ~ 30 h.
Beneficial effect
(1) poly-dopamine modified lithium carbon nanotube prepared by the present invention, it is easy to operate, it is easy to industrial amplification;
(2) poly-dopamine modified lithium carbon nanotube prepared by the present invention quickly, in the slave waste water of high dose can adsorb heavy metal Hg Ion.
Detailed description of the invention
Fig. 1 is adsorbance of the modified carbon nano-tube to mercury ion.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
The preparation of poly-dopamine modified lithium carbon nanotube, includes the following steps:
(1) pretreatment of carbon nanotube: take appropriate unmodified carbon nanotube in crucible, being placed in 350 DEG C of heating 30 in Muffle furnace Min removes agraphitic carbon impurity, and cooling, kept dry is spare;
(2) poly-dopamine modified lithium carbon nanotube: weighing 2.0 g of carbon nanotube in step (1), is ultrasonically treated 30 min, then claim 1.0 g dopamine hydrochlorides are taken, are placed in Tris-HCl (pH=8.5) buffer of 0.01 mol/L, room temperature (25 DEG C) magnetic Power stirs 24 h, is repeatedly washed through ultrapure water to neutrality, and the modified carbon nano-tube washed is done in 50 DEG C of vacuum ovens Dry 12 h, it is spare.
Embodiment 2
Modified carbon nano-tube includes the following steps: the adsorption experiment of mercury ion
100 mL of mercury ion solution of the mg/L of 30 mg/L ~ 400 is measured respectively in 150 mL beakers, accurately weighs more parts of changes 0.05 g modified carbon nano-tube, is put in beaker, adjust pH be 5, shake 3 h at room temperature, then detection absorption after mercury from Sub- concentration, is calculated as follows adsorbanceq e
q e=(C0-C1)V/m
In formula, C0、CtRespectively indicate ion concentration of mercury in initial soln (mg/L), C1For oscillation terminate rear solution in metal from Sub- concentration (mg/L),VFor the volume (L) of aqueous solution, m is the quality (g) of modified carbon nano-tube.
Fig. 1 reflects influence of the concentration to absorption, and the adsorbance of modified carbon nano-tube is with ion concentration of mercury in solution Increase and increase, until absorption reaches balance.When ion concentration of mercury is lower, the adsorbance of adsorbent is less, this may be because For at low concentrations, the adsorption site on modified carbon nano-tube is not fully utilized;And with the increase of ion concentration of mercury, absorption The adsorption site of unsaturated state in agent continues and mercury ion combines, to make adsorbance increase, until absorption reaches balance.From We can also be seen that adsorbent is 86.3 mg/g to the maximum saturation adsorbance of mercury ion in figure, illustrate absorption of the invention Agent is that a kind of adsorption capacity is big, efficient adsorbent for heavy metal.

Claims (8)

1. a kind of preparation method for the modified carbon nano-tube for removing mercury ions in waste water, including the following steps:
(1) pretreatment of carbon nanotube: take appropriate unmodified carbon nanotube in crucible, being placed in one timing of heating in Muffle furnace Between, agraphitic carbon impurity is removed, cooling, kept dry is spare;
(2) poly-dopamine modified lithium carbon nanotube: weighing the carbon nanotube in step (1), ultrasonic treatment, then weighs a certain amount of more Bar amine hydrochlorate, is placed in Tris-HCl buffer, room temperature magnetic agitation certain time, is repeatedly washed through ultrapure water to neutrality, The modified carbon nano-tube washed is dried into 8 ~ 12 h in a vacuum drying oven, it is spare.
2. a kind of preparation method of modified carbon nano-tube for removing mercury ions in waste water according to claim 1, feature It is, the temperature of the Muffle furnace as described in step (1) is 300 ~ 400 DEG C.
3. a kind of preparation method of modified carbon nano-tube for removing mercury ions in waste water according to claim 1, feature It is, the heating time as described in step (1) is 20 ~ 50 min.
4. a kind of preparation method of modified carbon nano-tube for removing mercury ions in waste water according to claim 1, feature It is, the quality of carbon nanotube described in the step (2) is 1.0 ~ 3.0 g.
5. a kind of preparation method of modified carbon nano-tube for removing mercury ions in waste water according to claim 1, feature It is, the time of the ultrasonic treatment of carbon described in the step (2) is 20 ~ 50 min.
6. a kind of preparation method of modified carbon nano-tube for removing mercury ions in waste water according to claim 1, feature It is, the quality of carbon dopamine hydrochloride described in the step (2) is 0.5 ~ 2.0 g.
7. a kind of preparation method of modified carbon nano-tube for removing mercury ions in waste water according to claim 1, feature It is, the concentration of Tris-HCl buffer described in the step (2) are as follows: 0.001 ~ 0.1 mol/L, pH value are 6 ~ 9.
8. a kind of preparation method of modified carbon nano-tube for removing mercury ions in waste water according to claim 1, feature It is, the time of room temperature magnetic agitation described in the step (2) are as follows: 10 ~ 30 h.
CN201811037520.4A 2018-09-06 2018-09-06 A kind of preparation method for the modified carbon nano-tube removing mercury ions in waste water Pending CN109052542A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113713630A (en) * 2021-04-20 2021-11-30 保定源汉升新材料科技有限公司 Composite membrane synthesis method for adsorbing gaseous mercury and composite membrane
CN114950154A (en) * 2022-05-12 2022-08-30 北京工业大学 Polydopamine modified carbon nanotube-graphene oxide membrane and preparation method and application thereof

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CN103012806A (en) * 2012-12-27 2013-04-03 复旦大学 Synthetic method and application of polydopamine-modified carbon nanotube composite material
CN104437358A (en) * 2014-10-20 2015-03-25 张亦彬 Process for preparing a composite adsorption material capable of simultaneously absorbing heavy metal ions and volatile organic substances in waste gas
CN105854846A (en) * 2016-06-23 2016-08-17 四川大学 Dopamine-modified adsorbent as well as preparation and application thereof
CN105879841A (en) * 2016-05-31 2016-08-24 河南师范大学 SiO2@PDA@ZIF-8 composite adsorbent for selectively adsorbing lead ions in wastewater and preparing method thereof
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CN104437358A (en) * 2014-10-20 2015-03-25 张亦彬 Process for preparing a composite adsorption material capable of simultaneously absorbing heavy metal ions and volatile organic substances in waste gas
CN105879841A (en) * 2016-05-31 2016-08-24 河南师范大学 SiO2@PDA@ZIF-8 composite adsorbent for selectively adsorbing lead ions in wastewater and preparing method thereof
CN105854846A (en) * 2016-06-23 2016-08-17 四川大学 Dopamine-modified adsorbent as well as preparation and application thereof
CN106830168A (en) * 2017-03-19 2017-06-13 兰州理工大学 A kind of method for efficiently removing heavy metal ion and organic matter in water removal
CN107523381A (en) * 2017-09-30 2017-12-29 陕西科技大学 A kind of preparation method of graphene carbon nanometer tube composite materials load nano copper particle lubriation material

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113713630A (en) * 2021-04-20 2021-11-30 保定源汉升新材料科技有限公司 Composite membrane synthesis method for adsorbing gaseous mercury and composite membrane
CN113713630B (en) * 2021-04-20 2023-09-19 保定源汉升新材料科技有限公司 Composite membrane synthesis method for adsorbing gaseous mercury and composite membrane
CN114950154A (en) * 2022-05-12 2022-08-30 北京工业大学 Polydopamine modified carbon nanotube-graphene oxide membrane and preparation method and application thereof

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Application publication date: 20181221