CN105363413B - A kind of multidimensional mesoporous metal organic framework sorbent and its application - Google Patents
A kind of multidimensional mesoporous metal organic framework sorbent and its application Download PDFInfo
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Abstract
The invention belongs to water treatment materials technical field, in particular to a kind of multidimensional mesoporous metal organic framework sorbent and its application in going water removal in the heavy metals such as arsenic, antimony.Multidimensional mesoporous metal organic framework sorbent of the invention is passed through obtained by self-assembling reaction as metal ion and organic ligand, during the reaction, by regulation coordination polymer size and its between bridge linking effect so that material have adaptation pore size and structure mesoporous multidimensional reticulated channel, specific surface area abundant and efficient activated adoption site.Multidimensional mesoporous metal organic framework sorbent of the invention can be used for drinking water, in industrial wastewater the heavy metals such as arsenic, antimony removal, arsenic, antimony concentration can achieve national standards for drinking water quality or industrial wastewater discharge standard requirements in treated water.
Description
Technical field
The invention belongs to water treatment materials technical field, in particular to a kind of multidimensional mesoporous metal organic framework sorbent
And its application in going water removal in the heavy metals such as arsenic, antimony.
Background technique
The advantages such as absorption method is at low cost with its, operational management facilitates and become removal water in heavy metal common technology.State
Inside and outside to have reported various heavy metal absorbents, there are also commercial prods in the market, but since adsorption capacity is low, the regeneration period
Frequently etc. factors and limit its and extensive be applied successfully.High-performance adsorbent material is developed for expanding adsorption technology in engineering
Using being of great significance.
Deeply recognize heavy metal adsorption mechanism and designs the active site being adapted to form of poluttants, duct based on this
Structure and absorption interface, this may be the important thinking to make a breakthrough in adsorbent development.But research in this regard both at home and abroad
It is still much insufficient with understanding.Firstly, absorbent interior duct formation mechenism is unclear, duct knot is difficult to realize in preparation process
Structure accurately controls, to limit the raising of adsorption site made full use of with pollutant duct diffusion rate.Secondly, heavy metal-polluted
It contaminates object and its different shape and recognizes deficiency in mechanism such as distribution, the adsorption and desorptions of solid liquid interface, be not able to achieve with form of poluttants
Based on adsorbent design and preparation.In addition, not yet establishing using form of poluttants and its conversion, adsorbent surface characteristic as base
The Adsorption technique for applying of plinth.The deficiency of above-mentioned fundamental aspect understanding makes it difficult to fundamentally efficient heavy be promoted to adsorb
The development of material, and further push the development and large-scale application of heavy metal removal technology.Metal-organic framework materials are close
A kind of porous material of Nian Lai academia discovery, specific surface area are up to 5000m2/ g or more is ideal adsorbent material.But
The metal-organic framework materials reported both at home and abroad are separated mainly for gas, store or are catalyzed, for the gold under water treatment system
Belong to organic framework material and its application is rarely reported.
The present invention handles problem for heavy metals such as arsenic, antimony in drinking water, industrial wastewater, develops a kind of high-performance multidimensional
Mesoporous metal organic framework sorbent, the adsorbent have many advantages, such as high specific surface area, adsorption capacity and the faster rate of adsorption,
It has a good application prospect in water process.
Summary of the invention
An object of the present invention is to provide a kind of performance efficiency for heavy metal contaminants such as arsenic antimony in water, be easy to answer
Multidimensional mesoporous metal organic framework sorbent.
The second object of the present invention is to provide multidimensional mesoporous metal organic framework sorbent in arsenic, antimony pollution water process
Using.
Technical principle of the invention is: the multiple tooth organic ligand of oxygen-containing, nitrogen such as 2-methylimidazole etc. is under suitable conditions
It can be with Zn2+Coordination occurs for equal transition metal ions, self-assembling reaction formation has large specific surface area, cellular structure moderate, active
Site multidimensional mesoporous metal organic framework sorbent abundant.The material has good absorption property to heavy metals such as arsenic antimony,
After being added in water can efficiently heavy metal in Adsorption water, then by solid-liquid separation unit go to remove water in suspended matter, water
Middle arsenic antimony is removed.
In order to prepare multidimensional mesoporous metal organic framework sorbent, the present invention is adopted the following technical scheme that:
(1) zinc solution, Acetate Solution and imidazole solution are prepared respectively；Wherein, in zinc solution and Acetate Solution
The molar ratio of zinc salt and acetate is 1:2~2:1；In zinc solution and imidazole solution the molar ratio of zinc salt and imidazoles be 1:15~
1: 40；
The zinc salt is one of zinc chloride, zinc sulfate, zinc nitrate, zinc formate, zinc acetate, zinc benzoate or one kind
The above mixture；
The acetate is one of sodium acetate, potassium acetate, ammonium acetate or more than one mixtures；
The imidazoles is 2-methylimidazole or 2-methylimidazole and 1- methylimidazole, 2- ethyl imidazol(e), methyl second
The mixture of one or both of base imidazoles, wherein ratio shared by 2-methylimidazole is 60% or more.
(2) zinc solution is mixed with Acetate Solution, solution ph is adjusted under the conditions of being sufficiently stirred to 4~8；
(3) under the conditions of being sufficiently stirred, the mixed solution of zinc salt and acetate is slowly equably added dropwise to 2- methyl miaow
In azoles solution；Stand 5~30 minutes；It further reacts 8~24 hours under slow stirring later；
The stirring condition is achieved by magnetic stirring apparatus or machine mixer；
Described is sufficiently stirred condition are as follows: when using magnetic stirrer, magneton revolving speed is in 300rpm or more；When adopting
When being stirred with machine mixer, rotating speed of agitator is in 150rpm or more；
Described is slowly stirred condition are as follows: when using magnetic stirrer, magneton revolving speed is between 50~150rpm；
When using machine mixer stirring, rotating speed of agitator is between 20~120rpm.
(4) solid is separated from solution using solid-liquid separating method, i.e. acquisition zinc-imidazole type multidimensional mesoporous metal is organic
Framework sorbent；The solid-liquid separating method can be centrifuge separation, film is separated by filtration or media filtration separation.
The invention also provides the application methods of above-mentioned multidimensional mesoporous metal organic framework sorbent:
Pending water pH value is adjusted to 7.0 or more；The absorption of multidimensional mesoporous metal organic backbone is added into pending water
Agent, throwing amount is between 0.01~1g/L；It is sufficiently mixed later, mixed reaction time is 0.5~10min；Later by solid
Liquid separate reactor removes suspended material in water removal, after drainage reaches standards for drinking water quality or industrial wastewater discharge standard excessively
Outflow；
The solid-liquid separating method can be one of precipitating, media filtration or film filtering or more than one group
It closes.
The present invention has following technical advantage:
1, sorbent preparation method and process are simple, do not need the reaction conditions such as high temperature and pressure, it is easy to accomplish；
2, adsorbent large specific surface area, compared with the high 2 times or more of Powdered Activated Carbon；
3, adsorbent is very high to the absorption property of heavy metal, much higher than the traditional adsorbent material reported both at home and abroad；
4, the application method of adsorbent is simple, does not need special reactor or reaction unit.
5, present invention can apply to the removal of the heavy metals such as arsenic antimony in drinking water, industrial wastewater, lake, water are applied also for
The removal of heavy metal in library, underground water.
Specific embodiment
Embodiment 1
The preparation of multidimensional mesoporous metal organic framework sorbent:
Liquor zinci chloridi, liquor kalii acetici and 2-methylimidazole solution are prepared respectively；Wherein, liquor zinci chloridi and potassium acetate
The molar ratio of zinc salt and acetate is 1:2 in solution；Zinc salt and 2-methylimidazole in liquor zinci chloridi and 2-methylimidazole solution
Molar ratio be 1:15；
Liquor zinci chloridi is mixed with liquor kalii acetici, (magneton revolving speed is 300rpm) is adjusted molten under the conditions of magnetic agitation
Liquid pH value is to 4；
(magneton revolving speed is 350rpm) under the conditions of magnetic agitation, the mixed solution of zinc chloride and potassium acetate is slowly uniform
Ground is added dropwise in 2-methylimidazole solution；Stand 5 minutes；Further (rotating speed of agitator is under the conditions of magnetic agitation later
150rpm) react 8 hours；
It is separated using centrifugal separation method, skims supernatant, obtain multidimensional mesoporous metal organic framework sorbent.
Applied to Removal of Arsenic in Drinking Water:
Pending water pH value is adjusted to 7.8；Multidimensional mesoporous metal organic framework sorbent is added into water, throwing amount is
0.05g/L；(rotating speed of agitator 200rpm) is sufficiently mixed under mechanical agitation, and mixed reaction time is
0.5min；Suspended material in water removal is gone by precipitating+media filtration later, filtering water outlet arsenic concentration reaches Drinking Water health mark
It is quasi-.
Embodiment 2
The preparation of multidimensional mesoporous metal organic framework sorbent:
Zinc nitrate solution, liquor kalii acetici are prepared respectively, prepare the mixed solution (2- of 2-methylimidazole and 1- methylimidazole
60%) methylimidazole ratio is；Wherein, the molar ratio of zinc salt and acetate is 2:1 in zinc nitrate solution and liquor kalii acetici；Nitre
The molar ratio of zinc salt and imidazoles is 1:40 in sour zinc solution and imidazole solution；
Zinc nitrate solution is mixed with liquor kalii acetici, (magneton revolving speed is 350rpm) is adjusted molten under the conditions of magnetic agitation
Liquid pH value is to 8；
It is under mechanical agitation (rotating speed of agitator 160rpm), the mixed solution of zinc nitrate and potassium acetate is slowly equal
It is added dropwise in imidazole solution evenly；Stand 5 minutes；Later further under mechanical agitation (rotating speed of agitator 20rpm)
Reaction 24 hours；
It is separated using Ultra filtration membrane method, obtains multidimensional mesoporous metal organic framework sorbent.
Antimony is removed applied to drinking water:
Pending water pH value is adjusted to 7.0；Multidimensional mesoporous metal organic framework sorbent is added into water, throwing amount is
0.2g/L；(rotating speed of agitator 150rpm) is sufficiently mixed under mechanical agitation, mixed reaction time 10min；
Suspended material in water removal is filtered off by film later, drainage antimony concentration is crossed and reaches standards for drinking water quality.
Embodiment 3
The preparation of multidimensional mesoporous metal organic framework sorbent:
Prepare zinc acetate solution, sodium acetate solution respectively, prepare 2-methylimidazole and 1- methylimidazole, 2- ethyl imidazol(e),
The mixed solution of Methylethyl imidazoles (2-methylimidazole ratio is 80%)；Wherein, zinc in zinc acetate solution and sodium acetate solution
The molar ratio of salt and acetate is 1:2；The molar ratio of zinc salt and imidazoles is 1:30 in zinc acetate solution and imidazole solution；
Zinc acetate solution is mixed with sodium acetate solution, (rotating speed of agitator 160rpm) is adjusted under mechanical agitation
Solution ph is to 8；
(magneton revolving speed is 320rpm) under the conditions of magnetic agitation, the mixed solution of zinc nitrate and sodium acetate is slowly uniform
Ground is added dropwise in imidazole solution；Stand 5 minutes；Further (magneton revolving speed is 150rpm) reaction under the conditions of magnetic agitation later
12 hours；
It is separated using micro-filtration membrane separating method, obtains multidimensional mesoporous metal organic framework sorbent.
Applied to industrial wastewater arsenic removal:
Pending water pH value is adjusted to 8.0；Multidimensional mesoporous metal organic framework sorbent is added into water, throwing amount is
1g/L；(rotating speed of agitator 180rpm) is sufficiently mixed under mechanical agitation, mixed reaction time 5min；Later
Partial suspended thing is removed by precipitation process first, successively filters off suspended matter in water removal by media filtration or film again later
Matter, filtering water outlet arsenic concentration reach industrial wastewater discharge standard.
Claims (4)
1. a kind of multidimensional mesoporous metal organic framework sorbent, it is characterized in that being prepared in accordance with the following steps:
(1) zinc solution, Acetate Solution and imidazole solution are prepared respectively；Wherein, zinc salt in zinc solution and Acetate Solution
Molar ratio with acetate is 1:2~2:1；The molar ratio of zinc salt and imidazoles is 1:15~1 in zinc solution and imidazole solution:
40；
The zinc salt is zinc chloride；
The acetate is one or both of sodium acetate, potassium acetate；
The imidazoles is 2-methylimidazole or 2-methylimidazole and 1- methylimidazole, 2- ethyl imidazol(e), Methylethyl miaow
The mixture of one or both of azoles, wherein ratio shared by 2-methylimidazole is 60% or more；
(2) zinc solution is mixed with Acetate Solution, solution ph is adjusted under the conditions of being sufficiently stirred to 4~8；
(3) under the conditions of being sufficiently stirred, the mixed solution of zinc salt and acetate is slowly equably added dropwise in imidazole solution；It is quiet
It sets 5~30 minutes；It further reacts 8~24 hours under slow stirring later；
(4) solid is separated from solution using solid-liquid separating method, i.e. acquisition zinc-imidazole type multidimensional mesoporous metal organic backbone
Adsorbent.
2. a kind of preparation method of multidimensional mesoporous metal organic framework sorbent according to claim 1, it is characterized in that:
The stirring condition is achieved by magnetic stirring apparatus or machine mixer；
Described is sufficiently stirred condition are as follows: when using magnetic stirrer, magneton revolving speed is in 300rpm or more；When the machine of using
When tool blender stirs, rotating speed of agitator is in 150rpm or more；
Described is slowly stirred condition are as follows: when using magnetic stirrer, magneton revolving speed is between 50~150rpm；When adopting
When being stirred with machine mixer, rotating speed of agitator is between 20~120rpm.
3. a kind of preparation method of multidimensional mesoporous metal organic framework sorbent according to claim 1, it is characterized in that: institute
The solid-liquid separating method stated is centrifuge separation, film is separated by filtration or media filtration separation.
4. a kind of application method of multidimensional mesoporous metal organic framework sorbent according to claim 1, it is characterized in that:
Pending water pH value is adjusted to 7.0 or more；Be added multidimensional mesoporous metal organic framework sorbent, throwing amount 0.01~
Between 1g/L；It is sufficiently mixed later, mixed reaction time is 0.5~10min；Later by being separated by solid-liquid separation reactor removal
Suspended material in water is crossed after drainage reaches standards for drinking water quality or industrial wastewater discharge standard and is flowed out；
The solid-liquid separating method is one of precipitating, media filtration or film filtering or more than one combination.
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| CN109414688A (en) * | 2016-05-27 | 2019-03-01 | 麻省理工学院 | The composition and correlation technique comprising metal organic framework absorbed for compound |
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| CN110229349A (en) * | 2019-07-17 | 2019-09-13 | 延边大学 | A kind of zeolite imidazole metalloid organic framework materials and its preparation method and application |
| CN110484527A (en) * | 2019-08-21 | 2019-11-22 | 清华大学 | A kind of deficiency metal organic framework-multienzyme complex and preparation method thereof and its application |
| CN111892715B (en) * | 2020-08-13 | 2021-04-16 | 广东泰金智能包装有限公司 | Metal organic framework material and preparation method and application thereof |
| CN114377654B (en) * | 2021-12-28 | 2023-04-07 | 生态环境部华南环境科学研究所 | Ammonia adsorption material for reducing ammonia volatilization amount and liquid surface covering ball thereof |
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