CN103055818A - Method for preparing metal-organic framework (MOF) porous absorbent material based on recycled waste - Google Patents
Method for preparing metal-organic framework (MOF) porous absorbent material based on recycled waste Download PDFInfo
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- CN103055818A CN103055818A CN2013100094023A CN201310009402A CN103055818A CN 103055818 A CN103055818 A CN 103055818A CN 2013100094023 A CN2013100094023 A CN 2013100094023A CN 201310009402 A CN201310009402 A CN 201310009402A CN 103055818 A CN103055818 A CN 103055818A
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Abstract
The invention discloses a method for preparing a metal-organic framework (MOF) porous absorbent material based on recycled waste. The method comprises the following steps of: recycling metal elements from batteries by using a wet treatment method to obtain metal salt solution; preparing solvothermal reaction solution; and crystallizing by using a solvothermal method.
Description
Technical field
The present invention relates to new material technology field, relate in particular to a kind of method for preparing the metal-organic framework porous adsorbing material based on the recovery waste product.
Background technology
Metal-the organic frame that grew up gradually in nearly ten years (metal-organic frameworks(MOF)) be with metal ion or metal cluster as frame joint, connect the crystalline structure of the spatial network that these nodes form by coordinate bond as skeleton with the organic molecule part.This material always can be by the design of molecule rank, the synthetic functionalization that realizes (comprising the modification of organic ligand and the doping of metal node) porous material, thereby the appearance of MOF is so that study from the exploratory stage to natural products porous material, go on the epoch of artificial design, greatly promoted the synthetic and application of new material.Before the MOF material is found, although foretold in theory the structure of up to a million possible porous systems, but for traditional zeolitic material, experimentally only found less than 200 structure (D.Bradshaw, Acc.Chem.Res.38 (2005) 273), and after the MOF system is found for over ten years, just have thousands of structures to be synthesized out, the number of the novel MOF material of annual report is pressed index law and is increased, and average per 3.5 years sums just double.
MOF is the lightest crystalline material of at present mankind's discovery, preparation, and this has benefited from its astonishing specific area.Specific area is to weigh the important parameter of porous material characteristic, and the specific area of traditional material mesolite class material generally only has hundreds of m
2/ g, active carbon then can reach thousands of m
2/ g, and the specific area of general MOF can reach several thousand m
2/ g.In identical surface area situation, the quality of MOF is than the low order of magnitude of traditional material, and this will save cost and the energy consumption of adsorbent production, transportation and post-processed greatly.As traditional porous material---annual overall market, the zeolite whole world is worth up to 3,500 hundred million dollars (Yaghi, Acc.Chem.Res.43 (2010) 58), yet the performance of zeolitic material is insuperior as can be known from above-mentioned material.Thereby the MOF material has huge application prospect and market potential as the substitute of zeolite.Although a large amount of novel MOF structures are synthesized out, and have showed goodish application potential, real real world applications also lags behind the exploitation of new material far away, and this situation all is very rare in the evolution in other materials field.Particularly the research and development for large-scale production technology are almost neglected fully.Norbert Stock points out in MOF material synthesis summary article in 2012: restriction MOF material really come into produce and life except new function and high-performance that present scientists is paid close attention to, the more important thing is that the following aspects is key point: utilizability and the cost of (1) material towards high yield, technical study cheaply; (2) synthesis condition; (3) technological process; (4) activation flow process; (5) productive rate; (6) purify; (7) reduce solvent and use (Chem.Rev.112 (2012) 933).Wherein primary be exactly cost and the availability of raw material be to realize the industrial key issue of MOF.
Along with popularizing of personal electric information products, society constantly increases for the demand of battery.The annual production of present national alkaline battery and lithium ion battery is near 5,000,000,000.Usually contain the mercury metal material of severe toxicity in the battery, thereby can not process with common land-fill method, constantly soaring battery production environment causes huge pressure.In recent years, popularize gradually without mercury and low mercury battery, although mercury-free battery can be according to common garbage disposal in principle, yet for mercury-free battery with to contain that mercury cell sorts itself be exactly a very large difficult problem.The more important thing is that the chief component composition is metal in the battery, its weight surpasses 50% of single weight.At present since the factor such as the immature and regenerant added value of product of recovery technology is low so that the recycling of battery even can not show a candle to macromolecular material causes the huge wasting of resources.
Summary of the invention
The technical problem that the present invention solves is for the cost of material problem of the large-scale production of metal-organic framework materials and the recycling problem of old and useless battery regenerant, decomposition, the material recovery of a cover from old and useless battery is provided, is purified to the synthetic method of metal-organic framework materials.The recycle used batteries added value of product of enterprise of lifting promotes large-scale production and the practical application of this high performance porous material of MOF.
In order to solve above technical problem, the embodiment of the invention discloses a kind of method based on reclaiming waste product and prepare the metal-organic framework porous adsorbing material, may further comprise the steps:
Select the metallic element in the wet processing recovery battery, obtain metal salt solution;
The solvent thermal reaction solution preparation;
With solvent thermal reaction solution dress still and solvent heat crystallization.
Further, as preferably, select the metallic element in the wet processing recovery battery, obtain metal salt solution and specifically comprise:
Disassemble battery, remove plastics and wrapper, adopt clear water that the product of disassembling is carried out neutral drip washing, remove the micro-K of solubility
+And Cl
-
Adopt the battery material after weak acid drip washing is disassembled to obtain to comprise Li
+, Zn
2+, Mg
2+, Co2+ and A1
3+, Cr
3+The metal salt solution mixture;
By adding extract, extract and separate is synthesized the required high pure metal salt of metal-organic frame;
For the Mn that is insoluble to weak acid
2+, Fe
2+, Cu
2+, add strong acid in the precipitation after drip washing and obtain Mn
2+, Fe
2+, Cu
2+Salting liquid, again extract, separate three kinds of salt.
Further, as preferably, weak acid is HNO
3Or H
2SO
4Or HCl.
Further, as preferably, the solvent thermal reaction solution preparation specifically comprises:
Metal salt solution and the organic molecule part of preparation are dissolved in the organic solvent, are mixed with solvent thermal reaction solution.
Further, as preferably, organic solvent comprises N, Ndimethylformamide or N, N-diethylformamide.
Further, as preferably, the organic molecule part comprises
Isosorbide-5-Nitrae-benzenedicarboxylate or triethylamine or 1,3,5-benzenetribenzoate or pyridine or trimesic acid or imidazoles or benzimidazole or
4-Methylimidazole or 2-Ethylimidazole or nitroimidazole.
Further, as preferably, solvent thermal reaction solution dress still and solvent heat crystallization are specifically comprised:
Get solvent thermal reaction solution and put into polytetrafluoroethyltank tank, sealing;
The tank of sealing is placed reactor, and then sealed reactor is heated to reactor 80 degrees centigrade of beginning first steps reaction 5 hours in drying box, generate crystal seed in solution; The temperature that then raises is carried out crystallization to 110-150 degree centigrade;
With solution filter, and clean with organic solvent with reaction after crystallization is finished, then use washed with de-ionized water; Natural drying in air atmosphere at last.
The present invention has reduced the cost of material of the large-scale production of metal-organic framework materials by decomposition, the material recovery that a cover old and useless battery is provided, the synthetic method that is purified to metal-organic framework materials, has improved the recycling rate of old and useless battery regenerant.
Description of drawings
When considered in conjunction with the accompanying drawings, by the following detailed description of reference, can more completely understand better the present invention and learn easily wherein many advantages of following, but accompanying drawing described herein is used to provide a further understanding of the present invention, consist of a part of the present invention, illustrative examples of the present invention and explanation thereof are used for explaining the present invention, do not consist of to improper restriction of the present invention, wherein:
Fig. 1 is a kind of method flow diagram for preparing the metal-organic framework porous adsorbing material based on the recovery waste product of the embodiment of the invention.
The specific embodiment
With reference to Fig. 1 embodiments of the invention are described.
For above-mentioned purpose, feature and advantage can be become apparent more, the present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
As shown in Figure 1, a kind of method based on reclaiming waste product and prepare the metal-organic framework porous adsorbing material may further comprise the steps:
S1, select wet processing to reclaim metallic element in the battery, obtain metal salt solution;
Disassemble battery, remove plastics and wrapper.Adopt clear water that the product of disassembling is carried out neutral drip washing, remove the micro-K of solubility
+And Cl
-Adopt weak acid (HNO
3, H
2SO
4Or HCl) battery material after drip washing is disassembled obtains to comprise Li
+, Zn
2+, Mg
2+, Co
2+And A1
3+, Cr
3+Etc. various metal salt solution mixtures.By adding extract, extract and separate is synthesized the required high pure metal salt of MOF.For the Mn that is insoluble to weak acid
2+, Fe
2+, Cu
2+, add strong acid in the precipitation after drip washing and obtain Mn
2+, Fe
2+, Cu
2+Salting liquid, again extract, separate three kinds of salt.
S2, hydro-thermal reaction solution preparation;
Metal salt solution and the organic molecule part of previous step preparation are dissolved in organic solvent (such as N, Ndimethylformamide(DMF), N, N-diethylformamide(EMF)) in, be mixed with hydro-thermal reaction liquid.Wherein organic ligand comprises
1,4-benzenedicarboxylate(1, the 4-phthalic acid), triethylamine (TMA), 1,3,5-benzenetribenzoate (BTB), pyridine (Py), trimesic acid (H3BTC), imidazoles, benzimidazole(benzimidazole), the 4-Methylimidazole(4 methylimidazole), the 2-Ethylimidazole(2 ethyl imidazol(e)), the nitroimidazole(nitroimidazole) etc. organic ligand molecule and derivative thereof.
S3, with hydro-thermal reaction solution dress still and solvent heat crystallization.
Get pretreated solution and put into polytetrafluoroethyltank tank, sealing.The tank of sealing is placed reactor, and then sealed reactor is heated to reactor 80 degrees centigrade of beginning first steps reaction 5 hours in drying box, generate crystal seed in solution.The temperature that then raises is carried out crystallization to 110-150 degree centigrade.Crystallization time is decided on different materials.After crystallization is finished with solution filter, and with the reaction clean with organic solvent.Then use washed with de-ionized water.Natural drying in air atmosphere at last.
Embodiment 1: the synthetic preparation zeolite type imidazoles framework take spent alkaline batteries as raw material-7(ZIF-7)
Disassemble the alkaline battery of recovery, remove plastics and iron packing, remove soluble impurity three times with the thing of disassembling of normal temperature clear water drip washing battery.The weak HNO of configuration
3Surplus materials after the neutral drip washing of solution (PH2) dissolving.Filter acid leacheate and remove precipitation, obtain Zn (NO
3)
2And Mn (NO
3)
2Mixed solution, can obtain in the battery 99% Zn element and 23% Mn element this moment in the solution.(part Mn element still in undissolved precipitation, extracts the Mn element and can further use concentrated acid dissolution precipitation thing).At 50 degrees centigrade of lower dissolving 20%bis-_2,4,4-trimethylpentyl phosphinic acid(CYANEX 272) extractant is in Escaid 110 extractants.The extract that in the acid leacheate that filters, adds preparation.Get the solution upper strata, further naturally dry solvent, obtain Zn (NO3) 24H of crystallization
2O is for subsequent use.
The solid mixture of 4 water zinc nitrates (3g) and benzimidazole (1g) is dissolved in stir in 100 milliliters the DMF solution and was made into hydro-thermal reaction liquid in 30 minutes.Hydro-thermal reaction liquid is put into polytetrafluoroethyltank tank, and place reactor, then sealed reactor is heated to reactor 80 degrees centigrade and did pre-crystallized reaction in 5 hours in drying box.Then the speed with 5 degrees centigrade of per minutes is warming up to 140 degrees centigrade of beginning crystallizations.Crystallization slowly was down to room temperature by the speed of 1 degree centigrade of per minute after 48 hours.After removing the mother liquor in the reactor, in reactor, add chloroform, collect clear crystal on the liquid upper strata, wash crystalline product three times with DMF solution, and under air atmosphere, naturally dry and namely obtain MOF crystal ZIF-7.Calculating productive rate by the Zn element is 50%.
Embodiment 2: utilize the lithium ion battery regenerant to prepare MOF crystal ZIF-12
Disassemble the lithium ion battery of recovery, remove plastic casing, remove soluble impurity with the thing of disassembling of normal temperature clear water drip washing battery (three times).The weak HNO of configuration
3The material of solution (1mol/l) after 75 degrees centigrade of neutral drip washing of lower dissolving 1 hour.Filter acid leacheate and remove precipitation, obtain LiNO
3And Co (NO
3)
2Mixed solution, can obtain in the battery 85% Li element and Co element this moment in the solution.Acid leacheate after the extraction of the 50 degrees centigrade of lower CYANEX of employing 272 extractants is filtered, adjusting pH value is 4.5, filters to obtain solution C o (NO
3)
2, under air atmosphere, naturally dry the Co (NO that obtains crystallization
3)
26H
2O is for subsequent use.
With Co (NO
3)
26H
2O and benzimidazole be the solid mixture of 1:3 preparation in mass ratio, is dissolved in to stir in 100 milliliters the DMF solution to be made into hydro-thermal reaction liquid in 30 minutes.Hydro-thermal reaction liquid is put into polytetrafluoroethyltank tank, and place reactor, then sealed reactor is heated to reactor 80 degrees centigrade and did pre-crystallized reaction in 1 hour in drying box.Then the speed with 5 degrees centigrade of per minutes is warming up to 130 degrees centigrade of beginning crystallizations.Crystallization slowly was down to room temperature by the speed of 1 degree centigrade of per minute after 48 hours.After removing the mother liquor in the reactor, on the reactor wall and the bottom collect clear crystal, wash crystalline product three times with DMF solution, and under air atmosphere, naturally dry and namely obtain MOF crystal ZIF-7.Calculate productive rate by the Co element and be about 40%.
Although more than described the specific embodiment of the present invention, but those skilled in the art is to be understood that, these specific embodiment only illustrate, those skilled in the art can carry out various omissions, replacement and change to the details of said method and system in the situation that does not break away from principle of the present invention and essence.For example, merge the said method step, then belong to scope of the present invention thereby carry out the identical function of essence according to the identical method of essence to realize the identical result of essence.Therefore, scope of the present invention is only limited by appended claims.
Claims (7)
1. one kind based on the method that reclaims waste product and prepare the metal-organic framework porous adsorbing material, it is characterized in that, may further comprise the steps:
Select the metallic element in the wet processing recovery battery, obtain metal salt solution;
The hydro-thermal reaction solution preparation;
With solvent thermal reaction solution dress still and solvent heat crystallization.
2. described method based on reclaiming waste product and prepare the metal-organic framework porous adsorbing material according to claim 1 is characterized in that, the described wet processing of selecting reclaims metallic element in the battery, obtains metal salt solution and specifically comprises:
Disassemble battery, remove plastics and wrapper, adopt clear water that the product of disassembling is carried out neutral drip washing, remove the micro-K of solubility
+And Cl
-
Adopt the battery material after weak acid drip washing is disassembled to obtain to comprise Li
+, Zn
2+, Mg
2+, Co
2+And A1
3+, Cr
3+The metal salt solution mixture;
By adding extract, extract and separate is synthesized the required high pure metal salt of metal-organic frame; For the Mn that is insoluble to weak acid
2+, Fe
2+, Cu
2+, add strong acid in the precipitation after drip washing and obtain Mn
2+, Fe
2+, Cu
2+Salting liquid, again extract, separate three kinds of salt.
3. described method based on reclaiming waste product and prepare the metal-organic framework porous adsorbing material according to claim 2 is characterized in that described weak acid is HNO
3Or H
2SO
4Or HCl.
4. described method based on reclaiming waste product and prepare the metal-organic framework porous adsorbing material according to claim 1 is characterized in that described hydro-thermal reaction solution preparation specifically comprises:
Metal salt solution and the organic molecule part of preparation are dissolved in the organic solvent, are mixed with solvent thermal reaction solution.
5. described method based on reclaiming waste product and prepare the metal-organic framework porous adsorbing material according to claim 4 is characterized in that described organic solvent comprises N, Ndimethylformamide or N, N-diethylformamide.
6. described method based on reclaiming waste product and prepare the metal-organic framework porous adsorbing material according to claim 4 is characterized in that described organic molecule part comprises
Isosorbide-5-Nitrae-benzenedicarboxylate or triethylamine or 1,3,5-benzenetribenzoate or pyridine or trimesic acid or imidazoles or benzimidazole or
4-Methylimidazole or 2-Ethylimidazole or nitroimidazole.
7. described method based on reclaiming waste product and prepare the metal-organic framework porous adsorbing material according to claim 1 is characterized in that, described solvent thermal reaction solution dress still and solvent heat crystallization is specifically comprised:
Get solvent thermal reaction solution and put into polytetrafluoroethyltank tank, sealing;
The tank of sealing is placed reactor, and then sealed reactor is heated to reactor 80 degrees centigrade of beginning first steps reaction 5 hours in drying box, generate crystal seed in solution;
The temperature that then raises is carried out crystallization to 110-150 degree centigrade;
With solution filter, and clean with organic solvent with reaction after crystallization is finished, then use washed with de-ionized water; Natural drying in air atmosphere at last.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237551A (en) * | 2015-10-09 | 2016-01-13 | 北京师范大学 | Zinc-based metal organic framework materials having room temperature phosphorescence characteristic and preparation method thereof |
| CN108676174A (en) * | 2018-06-07 | 2018-10-19 | 北京工业大学 | A method of preparing metal-organic framework materials using PET wastes |
| CN110407885A (en) * | 2019-08-02 | 2019-11-05 | 北京科技大学 | A method of metal-organic framework material is prepared using metallurgical mine solid waste |
| CN113444253A (en) * | 2020-03-24 | 2021-09-28 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework material and preparation method and application thereof |
| CN114583306A (en) * | 2022-03-01 | 2022-06-03 | 西安交通大学 | Method for recycling all elements of waste lithium iron phosphate batteries and preparing iron-based MOFs (metal-organic frameworks) material by organic acid integrated two-in-one double-effect |
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| CN101255495A (en) * | 2008-04-08 | 2008-09-03 | 上海电力学院 | Leaching method for recycling waste zinc-manganese alkaline dry batteries |
| CN101434612A (en) * | 2007-11-14 | 2009-05-20 | 中国科学院大连化学物理研究所 | Metal organic framework compound material, as well as preparation and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101434612A (en) * | 2007-11-14 | 2009-05-20 | 中国科学院大连化学物理研究所 | Metal organic framework compound material, as well as preparation and application thereof |
| CN101255495A (en) * | 2008-04-08 | 2008-09-03 | 上海电力学院 | Leaching method for recycling waste zinc-manganese alkaline dry batteries |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237551A (en) * | 2015-10-09 | 2016-01-13 | 北京师范大学 | Zinc-based metal organic framework materials having room temperature phosphorescence characteristic and preparation method thereof |
| CN108676174A (en) * | 2018-06-07 | 2018-10-19 | 北京工业大学 | A method of preparing metal-organic framework materials using PET wastes |
| CN110407885A (en) * | 2019-08-02 | 2019-11-05 | 北京科技大学 | A method of metal-organic framework material is prepared using metallurgical mine solid waste |
| WO2021022938A1 (en) * | 2019-08-02 | 2021-02-11 | 北京科技大学 | Method for preparing metal-organic framework using solid waste from metallurgical mine |
| CN113444253A (en) * | 2020-03-24 | 2021-09-28 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework material and preparation method and application thereof |
| CN113444253B (en) * | 2020-03-24 | 2022-06-21 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework material and preparation method and application thereof |
| CN114583306A (en) * | 2022-03-01 | 2022-06-03 | 西安交通大学 | Method for recycling all elements of waste lithium iron phosphate batteries and preparing iron-based MOFs (metal-organic frameworks) material by organic acid integrated two-in-one double-effect |
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Application publication date: 20130424 |