CN103664789B - A kind of method of magnetic Nano Graphene purifying ionic liquid - Google Patents
A kind of method of magnetic Nano Graphene purifying ionic liquid Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a kind of method of magnetic Nano Graphene purifying ionic liquid, comprise the steps: 1, prepare the graphene oxide of many base group modifications; 2, the Graphene of carried magnetic nano material is prepared by hydrothermal method; 3, with the impurity in magnetic Nano Graphene adsorbed ion liquid, purifying ionic liquid.Advantage of the present invention is the novel nano-material having a large amount of oxygen-containing functional groups (comprising hydroxyl, epoxy group(ing), carboxyl) with this surface of graphene oxide, magnetic is given to it, the magnetic carbon nano material (i.e. magnetic Nano Graphene) formed not only has the high characterization of adsorption of nano material, there is again the easily separated characteristic of magneticsubstance, with the ionic liquid purity after its process is high, Impurity removal is effective, simultaneously magnetic Nano Graphene can recycling, whole purge process is pollution-free, environmental protection, simple and feasible.
Description
Technical field
The present invention relates to a kind of method of purifying ionic liquid, particularly relate to a kind of method of magnetic Nano Graphene purifying ionic liquid, belong to applied chemistry and field of chemical engineering.
Background technology
Ionic liquid is a kind of green liquid material emerging over nearly 20 years, it is as organic molten salt, there is many compelling characteristics such as non-volatile, thermostability is high, electrochemical window is wide, easy ' cutting ' and functionalized design, paid close attention to and obtain important research progress widely in various fields such as chemistry, chemical industry, the energy, environment.The range of application of ionic liquid widely, different from typical organic solvent, electroneutral molecule is not had in ionic liquid, 100% is negatively charged ion and positively charged ion, all in liquid state between negative 100 DEG C to 200 DEG C, there is good thermostability and electroconductibility, allow kinetic control to a great extent; Concerning most of inorganics, organism and macromolecular material, ionic liquid is a kind of excellent solvent; Show acidity and super acids character, it not only can be used as solvent, but also can use as the catalyzer of some reaction, the solvent of these catalytic activitys avoids the shortcoming that extra possible poisonous catalyzer maybe may produce a large amount of waste; Ionic liquid generally can not become steam, so can not produce the obnoxious flavour polluted air in chemical experiment process; Price is relatively cheap, and most ionic liquid has stability to glassware for drinking water, easily prepares in aqueous phase; Ionic liquid also has excellent designability, can be obtained the ionic liquid of specific function by molecular designing.In a word, ionic liquid tasteless, ordorless, pollution-free, nonflammable, easily and product separation, easily reclaim, can repeated multiple timesly recycle, the advantage such as easy to use, it is the ideal substitute of traditional volatile solvent, it efficiently avoid the use of conventional organic solvents cause the problems such as serious environment, health, safety and equipment corrosion, be genuine, eco-friendly green solvent.Be suitable for current advocated cleaning technique and the requirement of Sustainable development, more and more by the extensive recognition and acceptance of people.
Ionic liquid in use can be mixed into impurity, such as, use ionic liquid Treating straw, and ionic liquid is known from experience mixed as the impurity such as xylogen, pigment.The ionic liquid function being mixed with impurity will reduce greatly, therefore be necessary to carry out purifying to ionic liquid.And ionic liquid cost is higher, therefore need to carry out recycling to ionic liquid.Traditional purification process needs repeatedly to clean ionic liquid, takes time and effort, cost is high.
Graphene is as a kind of type material, it is a kind of carbonaceous novel material of carbon atom tightly packed one-tenth individual layer bi-dimensional cellular shape crystalline network, the thickness of this Graphene crystal film only has 0.335nm, be hair diameter 200,000/, it is the material that intensity is the highest in the world known at present, be the elementary cell building other dimension carbonaceous material, there is fabulous crystallinity and chemical property.Because Graphene has these excellent performances, with low cost, the advantages such as workability is good, make it have great application prospect in fields such as electronics, information, the energy, material and biological medicines.
Summary of the invention
Goal of the invention: the method that the object of this invention is to provide a kind of magnetic Nano Graphene purifying ionic liquid fast and efficiently.
Technical scheme: the method for magnetic Nano Graphene purifying ionic liquid of the present invention, comprises the steps:
(1) graphene oxide of many base group modifications is prepared;
(2) Graphene of carried magnetic nano material is prepared by hydrothermal method;
(3) with the impurity in magnetic Nano Graphene adsorbed ion liquid, purifying ionic liquid.
In step (1), with the graphene oxide of Hummers legal system for many base group modifications.
In step (2), described magnetic Nano magneticsubstance is nano-sized iron oxide or nano-cerium oxide.
In step (3), the method for described purifying ionic liquid for add magnetic Nano Graphene and deionized water in ionic liquid, and whip attachment impurity wherein, then distills ionic liquid, removes moisture wherein, obtains the ionic liquid of purifying.Wherein, 300-500r/min stirs 30-40min at ambient temperature.
Meanwhile, after step (3), can reclaim magnetic Nano Graphene.Concrete recovery method is reclaim with magnet, and with solvent wash, then uses ultrasonication, removes the impurity of its absorption.Described solvent is dimethyl sulfoxide (DMSO).
Beneficial effect: the present invention compared with prior art, its remarkable advantage is: a large amount of oxygen-containing functional groups is contained on this for graphene oxide surface and (comprises hydroxyl, epoxy group(ing), carboxyl) novel nano-material, magnetic is given to it, the magnetic carbon nano material (i.e. magnetic Nano Graphene) formed not only has the high-specific surface area of nano material, the advantage of high characterization of adsorption, there is again the easily separated characteristic of magneticsubstance, high by the ionic liquid purity after its process, Impurity removal is effective, recyclable recycling, reduce costs, simultaneously magnetic Nano Graphene also can recycling, whole purge process is pollution-free, environmental protection, simple and feasible.
Embodiment:
Below technical scheme of the present invention is described further.
Embodiment 1: react according to following steps.
(1) with the standby graphene oxide being rich in multi-functional group of Hummers legal system
Measure the 46mL vitriol oil and 5.2ml phosphoric acid pours beaker into, beaker is put into ice bath and is cooled to less than 4 DEG C, and take 2g Graphite Powder 99 and put into beaker, 1h slowly adds 24g potassium permanganate later, and control temperature is no more than 10 DEG C, and the reaction times is about 2h altogether.Beaker is moved to thermostat water bath, and bath temperature controls, at 38 DEG C of reaction 0.5h, to keep stirring.In gained mixed solution, slowly add the distilled water of 100mL, keep mixeding liquid temperature 95 DEG C reaction 30min, period keeps appropriateness to stir; About 120mL deionized water stopped reaction is added after pyroreaction, add appropriate hydrogen peroxide (30Vol%) until do not produce bubble, question response is about 15min, adds the nitric acid of 20ml10%, and then adds the hydrochloric acid soln of 40mL (10Vol%).Filtration washing removes excessive acid and by product, is scattered in water by after washing in neutral graphite oxide, and sonic oscillation peels off 40min, and at the centrifugal 5min of 6000r/min after ultrasonic end, namely upper liquid is graphene oxide suspension liquid.Product-45 DEG C of vacuum lyophilizations, obtain the graphene oxide being rich in multi-functional group.
(2) graphene oxide of loaded with nano magnetic cerium is prepared by hydrothermal method
Get the graphene oxide 0.5g of the drying of above-mentioned preparation, be ground to fine powder, be scattered in water, sonic oscillation.Cerous acetate is dissolved in graphene oxide solution, adds a certain amount of tensio-active agent citric acid simultaneously, be exposed to half hour in air.Then under violent stirring condition, drip 0.1M sodium hydroxide or other highly basic to PH>9, stir suspension and present black, form cerium oxide nanoparicles and load to graphenic surface, obtain magnetic Nano Graphene.
Also can use nano-sized iron oxide load Graphene, concrete reaction process is: the graphene oxide 0.5g getting the above-mentioned drying prepared, is ground to fine powder, is scattered in water, sonic oscillation.Ferrous sulfate is dissolved in graphene oxide solution, adds a certain amount of tensio-active agent citric acid simultaneously, be exposed to half hour in air.Then under violent stirring condition, drip highly basic to PH>9, stir suspension and present black, form ferriferrous oxide nano-particle and load to graphenic surface, obtain magnetic Nano Graphene.
(4) magnetic Nano Graphene purifying ionic liquid
Get 1g magnetic Nano Graphene and add 100g used (containing impurity at least 3) ionic liquid [MMIM] [DMP], add 50ml deionized water, room temperature 400r/min stirs the impurity in 30min adsorbed ion liquid.Carry out 100 DEG C of underpressure distillation removing moisture after ionic liquid after purifying, obtain pure ionic liquid, detect the foreign matter content in ionic liquid before and after purifying.
The amount of impurity in ionic liquid before and after table 1 purifying
As shown in Table 1, purify ionic liquid with magnetic Nano Graphene, before purifying in ionic liquid containing impurity such as a small amount of xylogen, pigment and protein, after purifying, xylogen and pigment are all adsorbed, and its adsorption rate is 100%; A large amount of protein is adsorbed, and its adsorption rate is 93.9%.This illustrates that the nanostructure of Graphene can be combined with fiber, pigment impurity selectively, and does not affect the stabilising system of ionic liquid.
(5) method of the recovery of magnetic Nano Graphene
Graphene-supported nano magnetic material adopts magnet to reclaim quickly and efficiently, and then add solvent dimethyl sulfoxide (DMSO) (DMSO), we find that DMSO can remove pigment impurity, contribute to the recycling of magnetic graphene.Again magnetic Nano Graphene ultrasonic wave is processed 1h under 30w condition, remove the impurity of absorption, i.e. recyclable magnetic graphene.
Wherein, ultrasonic wave controls at 30-60w, and the treatment time controls at 1-1.5h.
Claims (7)
1. purify the method for ionic liquid with magnetic Nano Graphene, it is characterized in that comprising the steps:
(1) graphene oxide of many base group modifications is prepared;
(2) Graphene of carried magnetic nano material is prepared by hydrothermal method;
(3) with the impurity in magnetic Nano Graphene adsorbed ion liquid, purifying ionic liquid.
2. purify the method for ionic liquid according to claim 1 with magnetic Nano Graphene, it is characterized in that: in step (1), with the graphene oxide of Hummers legal system for many base group modifications.
3. purify the method for ionic liquid according to claim 1 with magnetic Nano Graphene, it is characterized in that: in step (2), described magnetic Nano material is nano-sized iron oxide or nano-cerium oxide.
4. the method for ionic liquid is purified according to claim 1 with magnetic Nano Graphene, it is characterized in that: in step (3), the method of described purifying ionic liquid for add magnetic Nano Graphene and deionized water in ionic liquid, whip attachment impurity wherein, then ionic liquid is distilled, remove moisture wherein, obtain the ionic liquid of purifying.
5. purify the method for ionic liquid according to claim 1 with magnetic Nano Graphene, it is characterized in that: after step (3), magnetic Nano Graphene is reclaimed.
6. purify the method for ionic liquid according to claim 5 with magnetic Nano Graphene, it is characterized in that: reclaim magnetic Nano Graphene with magnet, and with solvent wash, then use ultrasonication, remove the impurity that it adsorbs.
7. purify the method for ionic liquid according to claim 6 with magnetic Nano Graphene, it is characterized in that: described solvent is dimethyl sulfoxide (DMSO).
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| CN103947675B (en) * | 2014-04-11 | 2016-03-23 | 湖南大学 | Magnetic oxygenated graphene nanometer composite and its preparation method and application |
| CN104174359B (en) * | 2014-08-14 | 2016-05-18 | 同济大学 | Segregative Microscopic order graphene nano absorbent preparation method |
| CN104258810A (en) * | 2014-09-29 | 2015-01-07 | 扬州大学 | Adsorbing agent based on ferroferric oxide and graphene and preparation method of adsorbing agent |
| CN104356600B (en) * | 2014-11-24 | 2018-07-06 | 嘉兴学院 | A kind of high Interlaminar shear strengths carbon fibre composite and preparation method thereof |
| CN104839210A (en) * | 2015-03-24 | 2015-08-19 | 浙江工商大学 | Preparation method and application for magnetic-nanosilver-graphene nano composite material l |
| CN105524498A (en) * | 2016-01-23 | 2016-04-27 | 王秋芹 | Graphene ferric oxide base far infrared heating coating and preparation method thereof |
| CN109078613A (en) * | 2018-08-23 | 2018-12-25 | 苏州科技大学 | A kind of functional form magnetic ionic liquids graphene adsorbent and the preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747260A (en) * | 2009-12-24 | 2010-06-23 | 昆明理工大学 | Preparation method of ionic liquid |
| CN102671625A (en) * | 2012-05-02 | 2012-09-19 | 湖北富邦科技股份有限公司 | Method for preparing graphene magnetic nanometer composite materials |
| CN102989420A (en) * | 2012-12-11 | 2013-03-27 | 湖南大学 | Sulfonylation graphene oxide magnetic adsorbent, and preparation method and application thereof |
| CN103147169A (en) * | 2013-03-26 | 2013-06-12 | 宏远纺织科技（泉州）有限公司 | Method for recycling spinning ionic liquid through adopting activated carbon |
| CN103418383A (en) * | 2013-08-23 | 2013-12-04 | 江苏科技大学 | Magnetic nanometer oxidized graphene and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747260A (en) * | 2009-12-24 | 2010-06-23 | 昆明理工大学 | Preparation method of ionic liquid |
| CN102671625A (en) * | 2012-05-02 | 2012-09-19 | 湖北富邦科技股份有限公司 | Method for preparing graphene magnetic nanometer composite materials |
| CN102989420A (en) * | 2012-12-11 | 2013-03-27 | 湖南大学 | Sulfonylation graphene oxide magnetic adsorbent, and preparation method and application thereof |
| CN103147169A (en) * | 2013-03-26 | 2013-06-12 | 宏远纺织科技（泉州）有限公司 | Method for recycling spinning ionic liquid through adopting activated carbon |
| CN103418383A (en) * | 2013-08-23 | 2013-12-04 | 江苏科技大学 | Magnetic nanometer oxidized graphene and preparation method and application thereof |
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