CN102249363A - Method for using metal-organic framework material to purify water, exchange ions with water or magnetize water - Google Patents
Method for using metal-organic framework material to purify water, exchange ions with water or magnetize water Download PDFInfo
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- CN102249363A CN102249363A CN2011101961040A CN201110196104A CN102249363A CN 102249363 A CN102249363 A CN 102249363A CN 2011101961040 A CN2011101961040 A CN 2011101961040A CN 201110196104 A CN201110196104 A CN 201110196104A CN 102249363 A CN102249363 A CN 102249363A
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Abstract
The invention provides a method for using a metal-organic framework material to purify water, exchange ions with water or magnetize water and relates to the technical field of water treatment. The invention relates to a method for using the metal-organic framework material to purify water, exchange ions with water or magnetize water, to purity water and exchange ions with water, to purify water and magnetize water, to exchange ions with water and magnetize water, or to purify water, exchange ions with water and magnetize water. The metal-organic framework material contains pores, at least one metal ion and at least one organic compound, wherein the organic compound is at least bidentate and is bound (preferably, coordinately bound) with the metal ions. The invention also relates to a water purifier which contains the metal-organic framework material and is used for realizing the purpose. The method and the water purifier provided by the invention can be used for absorbing harmful substances in water, such as chlorine, peculiar smell, heterochrosis, peculiar odor matters, particle impurities, organic matters, chemical matters, heavy metal ions, and the like, achieving a function of purifying water and reducing the hardness of water. The metal-organic framework material contains ferromagnetic metal ions, thereby being capable of endowing water with magnetism.
Description
Technical field
The present invention relates to comprise the technical field of water treatment, relate in particular to the water purifier technology.The present invention be more particularly directed to use metal-organic framework materials to purify or the method for ion-exchange or magnetization or purification and ion-exchange or purification and magnetization or ion-exchange and magnetization or purification, ion-exchange and a kind of water of magnetization, this framework material comprises two at least coordinate organic compound of hole and at least a metal ion and at least a and described metal ion binding (preferred coordination binding), and relates to a kind of device that contains the material of above qualification.
Background technology
Water is people's indispensable a kind of materials of living, even can be described as one of human prerequisite from bottom to top.But Chinese most water pollution at present is serious, and traditional tap water treatment process can not guarantee to provide drink water; And in municipal water supply, also exist secondary pollution problem, as old tap water line of pipes, high-rise water tank etc. all can cause pollutions such as potential iron rust, incrustation scale and microorganism.
Owing to above reason, the water purifier of various brands arises at the historic moment.But the water purifier of prior art generally all need adopt the multilayer filter core, and active carbon layer adsorbs, and ion exchange layer plays bating effect, adds permanent magnet water is magnetic.When one deck filtering material is rotten, promptly influence the effluent quality of whole water purifier, and need to change all material, cause the wasting of resources.
Summary of the invention
Involved in the present invention, be to purify, or ion-exchange, or magnetization, or purification and ion-exchange, or purify and magnetization, or ion-exchange and magnetization, or purify, the method of ion-exchange and a kind of water of magnetization, it is characterized in that purifying by a kind of medium, or ion-exchange, or magnetization, or purification and ion-exchange, or purify and magnetization, or ion-exchange and magnetization, or purify, ion-exchange and a kind of water of magnetization, this medium comprises a kind of metal-organic framework materials, and this material contains two at least coordinate organic compound of porose and at least a metal ion and at least a and described metal ion binding (preferred coordination binding).
In addition, the present invention relates to a kind of equipment, the metal-organic framework materials of definition herein wherein is housed, is used for purifying or ion-exchange or magnetization or purification and ion-exchange or purification and magnetization or ion-exchange and magnetization or at least a water of purification, ion-exchange and magnetization.
Described equipment can also comprise following assembly in addition:
The container of metal-organic framework materials is housed;
Make at least a water can enter or leave the outlet/inlet of this equipment.
The present invention also further relates to a kind of water purification catridge, water purifier that medium described here is housed.
Also relate to the method that a kind of use comprises the medium of metal-organic framework materials described here, in fixing, mobile and mobile portable are used, preferably in family expenses water purifier, filtering type dixie cup, portable open-air water purification rod and direct-drinking water pipeline system, purify or ion-exchange or magnetization or purification and ion-exchange or purification and magnetization or ion-exchange and magnetization or at least a water of purification, ion-exchange and magnetization with this framework material.
The present invention has following at least a kind of advantage:
Granulometric impurity in chlorine in 1, can planar water, peculiar smell, heterochromatic, foreign odor thing and the water, organism,
Objectionable impurities such as chemical substance and heavy metal ion plays the effect of purifying waste water;
2, can remove Ca in the water by ion-exchange
2+, Mg
2+Plasma reduces water hardness;
3, contain ferromagnetic metal ion in the skeleton, can produce after being magnetized than high-intensity magnetic field, the charged particle in the water when this motion reaches certain intensity, just can make glassware for drinking water be magnetic because electromagnetic induction produces well-regulated rapid movement.
About the metal component in the framework material that is adopted according to invention, especially will should be mentioned that has main group in the periodictable, the metal ion of subgroup and group VIII element, wherein to should be mentioned that Mg especially, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Pb, As, Sb and Bi, more preferably Zn, Cu, Ni, Pd, Pt, Ru, Rh, In, Fe and Co.With regard to the metal ion of these elements, especially to should be mentioned that Mg
2+, Ca
2+, Sr
2+, Ba
2+, Sc
3+, Y
3+, La
3+, Ce
3+, Ce
4+, Pr
3+, Pr
4+, Nd
3+, Sm
3+, Sm
2+, Eu
3+, Eu
2+, Gd
3+, Tb
3+, Tb
4+, Dy
3+, Dy
4+, Ho
3+, Er
3+, Tm
3+, Tm
2+, Yb
3+, Yb
2+, Lu
3+, Ti
4+, Zr
4+, Hf
4+, V
4+, V
3+, V
2+, Nb
3+, Ta
3+, Cr
3+, Mo
3+, W
3+, Mn
3+, Mn
2+, Re
3+, Re
2+, Fe
3+, Fe
2+, Ru
3+, Ru
2+, Os
3+, Os
2+, Co
3+, Co
2+, Rh
2+, Rh
+, Ir
2+, Ir
+, Ni
2+, Ni
+, Pb
2+, Pd
+, Pt
2+, Pt
+, Cu
2+, Cu
+, Ag
+, Au
+, Zn
2+, Cd
2+, Hg
2+, Al
3+, Ga
3+, In
3+, Tl
3+, Si
4+, Si
2+, Ge
4+, Ge
2+, Sn
4+, Sn
2+, Pb
4+, Pb
2+, As
5+, As
3+, As
+, Sb
5+, Sb
3+, Sb
+And Bi
5+, Bi
3+, Bi
+
About can with two at least coordinate organic compound of metallic ion coordination, use all compounds that are applicable to this purpose and satisfy above-mentioned two at least these requirements of coordination in principle.Organic compound must have the metallic ion coordination of at least two energy and metal-salt, particularly with the center of top described metallic ion coordination.About two at least coordinate organic compound, to should be mentioned that compound especially with following structure:
I) aryl substructure contains 1 to 5 phenyl ring,
Ii) the alkyl substructure contains 1 to 10 carbon atom,
Iii) aryl or alkylamine substructure are made up of aryl that contains 1 to 5 phenyl ring or the alkyl that contains 1 to 10 carbon atom,
Iv) aryl or alkylphosphines substructure are made up of aryl that contains 1 to 5 phenyl ring or the alkyl that contains 1 to 10 carbon atom,
V) contain the heterocycle substructure of at least one heteroatoms (N, O, P, S, B, Si etc.), form by ternary or the above heterocycle of ternary,
Vi) contain the heterocycle benzo substructure of at least one heteroatoms (N, O, P, S, B, Si etc.), form by ternary or the above heterocycle of ternary,
Described substructure contains the functional group of at least a covalent bonding, for example, and CO
2H, CS
2H, NO
2, SO
3H, Si (OH)
3, Ge (OH)
3, Sn (OH)
3, Si (SH)
4, Ge (SH)
4, Sn (SH)
3, PO
3H, AsO
3H, AsO
4H, P (SH)
3, As (SH)
3, CH (RSH)
2, C (RSH)
3, CH (RNH
2)
2, C (RNH
2)
3, CH (ROH)
2, C (ROH)
3, CH (RCN)
2, C (RCN)
3And CH (SH)
2, C (SH)
3, CH (NH
2)
2, C (NH
2)
2, CH (OH)
2, C (OH)
3, CH (CN)
2And C (CN)
3The level of forming, wherein R is the alkylidene group with 1,2,3,4 or 5 carbon atom, or by 1 to 2 aryl that phenyl ring is formed.
Will should be mentioned that especially replacement or unsubstituted, monocycle or polycyclic fragrance two, three and quaternary carboxylic acid, and replacement or unsubstituted at least one heteroatoms imidazoles that comprises.
Particularly preferred part is a terephthalic acid, and particularly preferred metal ion is Cu
2+, Co
2+And Zn
2+
Except two at least coordinate organic compound, can also contain one or more can with the metal ion list coordinate part of metal-salt, preferred in principle under the coordinate material of itemizing:
A. comprise straight chain, side chain or cyclic aliphatic group, contain the alkylamine and the corresponding alkylammonium salt thereof of 1 to 20 carbon atom;
B. the arylamines and the corresponding aryl ammonium salt thereof that contain 1 to 5 phenyl ring;
C. comprise straight chain, side chain or cyclic aliphatic group, contain the alkylphosphines and the corresponding Wan Ji phosphonium salt thereof of 1 to 20 carbon atom;
D. the aryl phosphine and the corresponding Fang Ji phosphonium salt thereof that contain 1 to 5 phenyl ring;
E. comprise straight chain, side chain or cyclic aliphatic group, contain the alkyl organic acid and the corresponding alkyl organic anion (and salt) of 1 to 20 carbon atom;
F. contain the organic acid and the corresponding aryl organic anion (and salt) thereof of 1 to 5 phenyl ring aryl;
G. comprise straight chain, side chain or cyclic aliphatic group, contain the Fatty Alcohol(C12-C14 and C12-C18) of 1 to 20 carbon atom;
H. the aryl alcohol that contains 1 to 5 phenyl ring;
I. inorganic anion can comprise following:
The group that nitrate, nitrite, vitriol, sulphite, hydrosulphite, phosphoric acid salt, hydrophosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, muriate, oxymuriate, bromide, bromate, iodide, iodate, carbonate, supercarbonate and the corresponding acid of above-mentioned inorganic anion and salt are formed;
J. ammonia, carbonic acid gas, methane, oxygen, ethene, hexane, benzene,toluene,xylene, chlorobenzene, oil of mirbane, naphthalene, thiophene, pyridine, propyl alcohol, 1,2-ethylene dichloride, methylene dichloride, tetrahydrofuran (THF), thanomin, triethylamine and trifluoromethanesulfonic acid.
Further details about preferred metal ion, two at least coordinate organic compound and single coordination organic compound can get from the EP-A0790253 inference, introduces the reference of its associated viscera as the application here.
Below by the mode of giving an example, list metal-organic framework materials synthetic and that characterize.
In the application's the framework material, especially preferred is to comprise Zn
2+As metal ion with derived from VITAMIN B4,4, the part of 4-diphenyl dicarboxylic acid is called bio-MOF-1 as the framework material of coordination compound in the document.
As to be clean and/or ion-exchange and/or magnetized water, need should be mentioned that tap water, earth surface water source and underground water source especially.Tap water can reach the standard of tap water after treatment.
Description of drawings
Fig. 1 represents the X-ray powder diffraction pattern by the bio-MOF-1 framework material of embodiment 1 preparation.
Specific implementation method
Be used to prepare the preparation method of the used framework material of the present invention, be disclosed in J.Am.Chem.Soc.2009 especially, 131, among the 8376-8277. from crystalline mother solution, separate framework material, particularly bio-MOF-1, can adopt method well known in the art to carry out.Framework material after the separation can mix by known method in the plastic working, fusion, extrude, co-extrusion, stamping, spinning, foaming and granulation.
Embodiment 1 (preparation of bio-MOF-1)
With above-mentioned starting material with as the 13.5ml N of solvent, dinethylformamide (DMF), 1ml water are put into the autoclave of the inner liner polytetrafluoroethylene of 20ml successively.Heating is 24 hours under 130 ℃ of conditions.And be cooled to room temperature gradually, promptly obtain bar-shaped clear crystal.With crystal DMF (3ml) rinse three times.In ar gas environment dry 30 minutes then.
Then, measure the feature of describing products therefrom by X-ray powder diffraction.Products therefrom shows X-ray powder diffraction figure as shown in Figure 1, and is consistent with bio-MOF-1.
Embodiment 2 (ion-exchange of bio-MOF-1)
Take by weighing that gained bio-MOF-1 0.35g joins in EtOH/H2O (15ml/5ml) solution of the lithium nitrate of 20ml 0.1mol/L among the embodiment 1, at room temperature soak 48h, and wherein changed one time fresh solution in 24 hours, use the lithium nitrate of ethanol drip washing several then with the flush away surface, naturally dry, promptly get the bio-MOF-1. of Li ion-exchange
Purifying method involved in the present invention is used smelling in the metal-organic framework materials planar water, flavor, colourity, chlorination organism, agricultural chemicals, radioactivity organism and other artificial synthetic organic materials, in order to purifying water body; And the method by ion-exchange has reduced water hardness, can reach special use and the treatment effect requirement of tap water purification process to water-purifying material.
The above is only for preferred embodiment of the present invention, in any change that does not exceed the present invention and made, and the scope that still belongs to the present invention and comprised.
Claims (9)
1. with the method for metal-organic framework materials purification, ion-exchange or magnetized water, it is characterized in that: act on water by a kind of dense-medium purification that comprises metal-organic framework materials or ion-exchange or magnetized water or three's arbitrary combination, this metal-organic framework materials comprises two at least coordinate organic compound of hole and at least a metal ion and at least a and described metallic ion coordination binding.
2. method according to claim 1 is characterized in that described water relates at least a of following water: tap water, earth surface water source and underground water source.
3. method according to claim 2, wherein said earth surface water source and underground water source relate to rivers, lake, reservoir, seawater and diving, piestic water, crack lava water, perched water and spring.
4. method according to claim 1 is characterized in that two at least coordinate organic compound are selected from polycarboxylic aromatic acids at least a replacement or unsubstituted, that contain one or more rings; And replacement or unsubstituted, comprise at least one heteroatoms and can contain the polycarboxylic aromatic acids of one or more rings; And replacement or unsubstituted imidazoles organism.
5. method according to claim 1 is characterized in that described metal ion is the metal ion that is selected from all main groups in the periodic table of elements, subgroup and group VIII element.
6. method according to claim 1 is characterized in that metal-organic framework materials is to comprise Zn
2+As metal ion with derived from VITAMIN B4,4, the part of 4-diphenyl dicarboxylic acid is as the framework material of coordination compound.
7. method according to claim 1 is used for fixing, moves and mobile portable purifies in using or ion-exchange or magnetization or purification and ion-exchange or purify and magnetization or ion-exchange and magnetization or purification, ion-exchange and magnetized water.
8. method according to claim 1 is applied to household water filter, filtering type dixie cup, portable open-air water purification rod and direct-drinking water pipeline system.
9. method according to claim 1 is used for household water filter, filtering type dixie cup, portable open-air water purification rod and direct-drinking water pipeline system.
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Cited By (15)
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|---|---|---|---|---|
| CN102745765A (en) * | 2012-07-31 | 2012-10-24 | 重庆三峡学院 | Method for treating waste water containing phenol by coordination polymer |
| CN103100373A (en) * | 2013-02-26 | 2013-05-15 | 河南师范大学 | Adsorbent, preparation method and application thereof |
| CN104817124A (en) * | 2015-05-12 | 2015-08-05 | 景焕粒子能科技发展有限公司 | Composite material for preparing particle-energy multifunctional activated water and preparation method and device of composite material |
| CN105214612A (en) * | 2015-09-18 | 2016-01-06 | 北京化工大学 | A kind of application of metal-organic framework functionalization material |
| CN105642238A (en) * | 2016-02-26 | 2016-06-08 | 北京化工大学 | Preparation method and application of SiO2@MIL-68 (Al) composite material |
| WO2017096638A1 (en) * | 2015-12-07 | 2017-06-15 | 中国科学院生态环境研究中心 | Manganese dioxide nanofiber @ multidimensional mesoporous metal-organic framework adsorbent and preparation therefor |
| CN106861461A (en) * | 2016-12-29 | 2017-06-20 | 中国科学院长春应用化学研究所 | A kind of hydroxyl modified MOF films removed to heavy metal ion high definition in blood and preparation method thereof |
| WO2017127593A1 (en) * | 2016-01-20 | 2017-07-27 | Youngstown State University | Metal organic framework with perfluorinated linker |
| US10266435B2 (en) | 2015-05-12 | 2019-04-23 | Jinghuan Particle Energy Technology Development Co., Ltd. | Composite material, method and device for preparing particle-energy multifunctional active water |
| CN110591111A (en) * | 2019-10-14 | 2019-12-20 | 齐鲁工业大学 | Controllable dynamic tuning random laser scattering material based on metal-organic framework nanocrystalline, laser device, preparation method and application |
| CN110922606A (en) * | 2019-12-23 | 2020-03-27 | 北京工业大学 | Microporous Cu-MOF metal organic framework material constructed by adenine and auxiliary ligand, preparation and application |
| CN112280054A (en) * | 2020-10-30 | 2021-01-29 | 浙江理工大学 | Yttrium-based metal-organic framework material and application thereof |
| US11253837B2 (en) | 2016-04-22 | 2022-02-22 | The Regents Of The University Of California | Post-synthetically modified metal-organic frameworks for selective binding of heavy metal ions in water |
| US11565235B2 (en) * | 2017-07-19 | 2023-01-31 | Youngstown State University | System and method for removing contaminants |
| CN116284811A (en) * | 2023-02-05 | 2023-06-23 | 吉林大学 | Preparation method and application of Ga-MOGs |
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| JIHYUN AN ET AL: "Cation-Triggered Drug Release from a Porous Zinc-Adeninate Metal-Organic Framework", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 》, vol. 131, no. 24, 2 June 2009 (2009-06-02), pages 8376 - 8377, XP002693316, DOI: doi:10.1021/ja902972w * |
Cited By (22)
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|---|---|---|---|---|
| CN102745765A (en) * | 2012-07-31 | 2012-10-24 | 重庆三峡学院 | Method for treating waste water containing phenol by coordination polymer |
| CN103100373A (en) * | 2013-02-26 | 2013-05-15 | 河南师范大学 | Adsorbent, preparation method and application thereof |
| CN104817124A (en) * | 2015-05-12 | 2015-08-05 | 景焕粒子能科技发展有限公司 | Composite material for preparing particle-energy multifunctional activated water and preparation method and device of composite material |
| US10266435B2 (en) | 2015-05-12 | 2019-04-23 | Jinghuan Particle Energy Technology Development Co., Ltd. | Composite material, method and device for preparing particle-energy multifunctional active water |
| CN105214612B (en) * | 2015-09-18 | 2019-01-04 | 北京化工大学 | A kind of application of metal-organic framework functionalization material |
| CN105214612A (en) * | 2015-09-18 | 2016-01-06 | 北京化工大学 | A kind of application of metal-organic framework functionalization material |
| WO2017096638A1 (en) * | 2015-12-07 | 2017-06-15 | 中国科学院生态环境研究中心 | Manganese dioxide nanofiber @ multidimensional mesoporous metal-organic framework adsorbent and preparation therefor |
| US10450205B2 (en) | 2016-01-20 | 2019-10-22 | Youngstown State University | Metal organic framework with perfluorinated linker |
| WO2017127593A1 (en) * | 2016-01-20 | 2017-07-27 | Youngstown State University | Metal organic framework with perfluorinated linker |
| CN105642238B (en) * | 2016-02-26 | 2018-05-25 | 北京化工大学 | A kind of SiO2The preparation method and application of@MIL-68 (Al) composite material |
| CN105642238A (en) * | 2016-02-26 | 2016-06-08 | 北京化工大学 | Preparation method and application of SiO2@MIL-68 (Al) composite material |
| US11253837B2 (en) | 2016-04-22 | 2022-02-22 | The Regents Of The University Of California | Post-synthetically modified metal-organic frameworks for selective binding of heavy metal ions in water |
| CN106861461B (en) * | 2016-12-29 | 2019-06-04 | 中国科学院长春应用化学研究所 | The hydroxyl modified MOF film and preparation method thereof that heavy metal ion high definition is removed in a kind of pair of blood |
| CN106861461A (en) * | 2016-12-29 | 2017-06-20 | 中国科学院长春应用化学研究所 | A kind of hydroxyl modified MOF films removed to heavy metal ion high definition in blood and preparation method thereof |
| US11565235B2 (en) * | 2017-07-19 | 2023-01-31 | Youngstown State University | System and method for removing contaminants |
| CN110591111A (en) * | 2019-10-14 | 2019-12-20 | 齐鲁工业大学 | Controllable dynamic tuning random laser scattering material based on metal-organic framework nanocrystalline, laser device, preparation method and application |
| CN110591111B (en) * | 2019-10-14 | 2022-02-25 | 齐鲁工业大学 | Controllable dynamic tuning random laser scattering material based on metal-organic framework nanocrystalline, laser device, preparation method and application |
| CN110922606A (en) * | 2019-12-23 | 2020-03-27 | 北京工业大学 | Microporous Cu-MOF metal organic framework material constructed by adenine and auxiliary ligand, preparation and application |
| CN110922606B (en) * | 2019-12-23 | 2022-04-19 | 北京工业大学 | Microporous Cu-MOF metal organic framework material constructed by adenine and auxiliary ligand, preparation and application |
| CN112280054A (en) * | 2020-10-30 | 2021-01-29 | 浙江理工大学 | Yttrium-based metal-organic framework material and application thereof |
| CN116284811A (en) * | 2023-02-05 | 2023-06-23 | 吉林大学 | Preparation method and application of Ga-MOGs |
| CN116284811B (en) * | 2023-02-05 | 2024-05-28 | 吉林大学 | Preparation method and application of Ga-MOGs |
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Application publication date: 20111123 |