CN107376853A - A kind of@MG composite adsorbing materials of ZIF 8 for selective absorption Cu in waste water ion - Google Patents

A kind of@MG composite adsorbing materials of ZIF 8 for selective absorption Cu in waste water ion Download PDF

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Publication number
CN107376853A
CN107376853A CN201710766093.2A CN201710766093A CN107376853A CN 107376853 A CN107376853 A CN 107376853A CN 201710766093 A CN201710766093 A CN 201710766093A CN 107376853 A CN107376853 A CN 107376853A
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zif
composite adsorbing
adsorbing materials
selective absorption
waste water
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CN107376853B (en
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叶存玲
王慎
王远飞
王治科
范顺利
陈凌云
李玮利
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Henan Normal University
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Henan Normal University
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    • 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
    • B01J20/223Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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)
  • Hydrology & Water Resources (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Sorption (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a kind of@MG composite adsorbing materials of ZIF 8 for selective absorption Cu in waste water ion, the@MG composite adsorbing materials of ZIF 8 can from the copper-containing wastewater coexisted with Cd (II), Ni (II), Mn (II), Co (II), Mg (II) and Cr (VI) selective absorption Cu (II), and specifically disclose the preparation method of the@MG composite adsorbing materials of ZIF 8.The@MG composite adsorbing materials of ZIF 8 of the present invention can be in selective absorption waste water copper ion, adsorbance is big, and absorption of the common metal ion to copper ion is not disturbed, and the adsorption cleaning available for copper-containing wastewater is handled.

Description

A kind of ZIF-8@MG composite adsorbing materials for selective absorption Cu in waste water ion
Technical field
The invention belongs to compound adsorbent technical field, and in particular to a kind of for selective absorption Cu in waste water ion ZIF-8@MG composite adsorbing materials.
Background technology
Copper-containing wastewater is mainly derived from the industry such as exploitation and smelting, medicine, dyestuff, plating and the intermetallic composite coating of copper zinc ore. Although copper is trace element necessary to human body, when remaining substantial amounts of copper in human body, the liver in human body and courage can be made Into burden, it may appear that metabolic disturbance, cause hepatic sclerosis, liver ascites etc..Copper can also damage nervous system, cause multiple god Through inflammation, neurasthenia etc..
The method of common processing heavy metal ions in wastewater mainly have chemical precipitation method, ion-exchange, electrolysis and Absorption method etc., wherein absorption method are due to having the advantages that efficient, cost is low and cannot be easily caused secondary pollution and is widely used. The common material as adsorbent active charcoal, zeolite molecular sieve, oxide and metal-organic framework materials etc..Class zeolite imidazole Ester framework material(Zeolitic imidazolate frameworks, ZIFs)Be one kind by imidazoles or imdazole derivatives and gold It is mainly Zn to belong to ion2+、Co2+Deng the metal-organic framework materials of composition.ZIFs not only has the topological type knot similar to zeolite Structure, and its good hydrothermal stability, prolonged seethe with excitement will not also cave in water and organic solvent.
ZIF-8 belongs to class zeolitic imidazolate framework material(ZIFs)One kind, be by the Zn in zinc salt2+With 2-methylimidazole A kind of material with zeolite SOD type topological structure of ligand reaction generation, each zinc atom and four 2- methyl in its structure Nitrogen-atoms on imidazole ring is coordinated to form a ZnN with positive tetrahedron structure4Cluster, can be with as node using these clusters Imidazole ring on 2-methylimidazole, which is connected, forms a cage coordination compound with regular hexahedron crystal formation.ZIF-8 have compared with High specific surface area, aperture controllable, the advantages that being easy to carry out its structure modulation and modification, it is used for as adsorbent ZIF-8 The Adsorption of the pollutants such as Wastewater Dyes, heavy metal is got the attention.
The content of the invention
Present invention solves the technical problem that it there is provided a kind of ZIF-8@MG for selective absorption Cu in waste water ion Composite adsorbing material, the ZIF-8@MG composite adsorbing materials use as adsorbent, and separation process is easy to operate, avoids tradition Powder, granular adsorbent needs the tediously long operating process such as filtered, centrifuged.
The present invention for solve above-mentioned technical problem adopt the following technical scheme that, one kind be used for selective absorption Cu in waste water from The ZIF-8@MG composite adsorbing materials of son, it is characterised in that:The ZIF-8@MG composite adsorbing materials can from Cd (II), Ni (II), selective absorption Cu (II) in the copper-containing wastewater that Mn (II), Co (II), Mg (II) and Cr (VI) coexist, the ZIF-8@MG The specific preparation process of composite adsorbing material is:MG is cut into 20 of 2cm × 2cm and with the hydroxide that mass concentration is 20% Sodium solution soaks 2h, then gauze is swung with deionized water and is washed till close to neutrality, is subsequently placed in drying box and is obtained in 70 DEG C of drying 10h MG after to alkalization is standby;By 2.346g Zn (NO3)2·6H2O is dissolved in 8mL distilled water, and the MG added after alkalization forms mixed Zoarium system, 22.6g 2-methylimidazoles are dissolved in 80mL distilled water and the solution of formation is added in mixed system, are sealed After be placed in Clothoid type water-bath constant temperature oscillator and vibrate 24h under conditions of 30 DEG C, 120r/min, then take out and stand 24h, most Gauze is swung with deionized water afterwards and washed 4-5 times, and ZIF-8 MG composite adsorbing materials are made in 70 DEG C of drying.
The ZIF-8@MG composite adsorbing materials of the present invention can be in selective absorption waste water copper ion, adsorbance is big, and And absorption of the common metal ion to copper ion is not disturbed, the adsorption cleaning available for copper-containing wastewater is handled.
Brief description of the drawings
Fig. 1 is MG and ZIF-8@MG infrared spectrum;
Fig. 2 is ZIF-8, MG and ZIF-8@MG XRD;
Fig. 3 is ZIF-8 SEM figures;
Fig. 4 is MG SEM figures;
Fig. 5 is ZIF-8@MG SEM figures;
Fig. 6 is adsorption time to ZIF-8@MG composite adsorbing material absorption property influence curves.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair Bright scope.
Embodiment 1
1st, the preparation of ZIF-8@MG composite adsorbing materials:
MG is cut into 20 of 2cm × 2cm and soaks 2h with the sodium hydroxide solution that mass concentration is 20%, then gauze is spent It is standby that ion pond is washed till the MG close to neutrality, being subsequently placed in drying box after 70 DEG C of drying 10h are alkalized;By 2.346g Zn(NO3)2·6H2O is dissolved in 8mL distilled water, and the MG added after alkalization forms mixed system, by 22.6g 2-methylimidazoles It is dissolved in 80mL distilled water and the solution of formation is added in mixed system, Clothoid type water-bath constant temperature oscillator is placed in after sealing In vibrate 24h under conditions of 30 DEG C, 120r/min, then take out stand 24h, finally gauze is swung with deionized water and washes 4-5 It is secondary, and ZIF-8@MG composite adsorbing materials are made in 70 DEG C of drying.In addition, being used to characterize control, MG is being added without, it is other In the case that experiment condition keeps constant, ZIF-8 is synthesized.
2nd, characterize:
Fig. 1 is ZIF-8, MG and ZIF-8@MG infrared spectrum.Except observing MG feature in ZIF-8@MG infrared spectrums Outside absworption peak, there are ZIF-8 characteristic absorption peaks, such as in 3329.75cm-1And 1568.71cm-1There is methylimidazole ring in place In c h bond stretching vibration peak, this explanation ZIF-8 be successfully bonded on MG.
Fig. 2 is ZIF-8, MG and ZIF-8@MG XRD.Observed in ZIF-8@MG XRD spectra corresponding with ZIF-8 Consistent characteristic diffraction peak, this explanation ZIF-8@MG preparation is without the crystal structure for destroying ZIF-8.
Fig. 3-5 is respectively ZIF-8, MG and ZIF-8@MG SEM figures.ZIF-8 distribution of particles is than more uniform, MG and ZIF- There were significant differences for 8@MG patterns, and this shows that ZIF-8@MG are successfully prepared.
3rd, selectivity experiment:
Respectively toward 50mL concentration be in 50mg/L Cu (II), Pb (II), Cd (II), Mn (II), Co (II), Cr (VI) solution plus Enter ZIF-8@MG composite adsorbing material 20mg, with 160r/min speed oscillation 8h in 30 DEG C of water-bath constant temperature oscillator.By Table 1 understands that ZIF-8@MG composite adsorbing materials are smaller to Pb (II), Cd (II), Mn (II), Co (II), Cr (VI) adsorbance, But notable to Cu (II) adsorption effect, adsorbance is up to 60.9mg/g.
The adsorptive selectivity of the ZIF-8@MG composite adsorbing materials of table 1
4th, interference experiment:
It is 50mg/L to weigh 20mg ZIF-8@MG composite adsorbing materials respectively and be added to Cu (II) with interfering ion initial concentration 50mL solution in, in 30 DEG C of speed oscillation 8h with 160r/min, experimental result is shown in Table 2.As Cu (II) and interfering ion Ni (II) when and Co (II) coexists, absorption of the ZIF-8@MG composite adsorbing materials to Cu (II) is barely affected.Work as interfering ion For Cd (II), Mn (II), Mg (II), Cr (VI) when, ZIF-8@MG composite adsorbing materials dramatically increase to Cu (II) adsorbance.
The absorption interference free performance of the ZIF-8@MG composite adsorbing materials of table 2
5th, the adsorption dynamics adsorption kinetics of ZIF-8@MG composite adsorbing materials:
It is in 50mg/L Cu (II) solution, in 30 to weigh 20mg ZIF-8@MG composite adsorbing materials and be added to 50mL initial concentrations DEG C with 160r/min speed oscillation.It will be appreciated from fig. 6 that ZIF-8@MG composite adsorbing materials are fast to Cu (II) rate of adsorption, 300min reaches adsorption equilibrium.

Claims (1)

  1. A kind of 1. ZIF-8@MG composite adsorbing materials for selective absorption Cu in waste water ion, it is characterised in that:It is described ZIF-8@MG composite adsorbing materials can be from coexisting with Cd (II), Ni (II), Mn (II), Co (II), Mg (II) and Cr (VI) Selective absorption Cu (II) in copper-containing wastewater, the specific preparation process of the ZIF-8@MG composite adsorbing materials are:MG is cut into 2cm 20 of × 2cm and soak 2h with the sodium hydroxide solution that mass concentration is 20%, then gauze swung with deionized water be washed till it is close Neutrality, the MG being subsequently placed in drying box after 70 DEG C of drying 10h are alkalized are standby;By 2.346g Zn (NO3)2·6H2O is molten In 8mL distilled water, the MG added after alkalization forms mixed system, and 22.6g 2-methylimidazoles are dissolved in 80mL distilled water And the solution of formation is added in mixed system, it is placed in after sealing in Clothoid type water-bath constant temperature oscillator in 30 DEG C, 120r/ 24h is vibrated under conditions of min, then takes out and stands 24h, finally gauze is swung with deionized water and washed 4-5 times, and in 70 DEG C of drying ZIF-8@MG composite adsorbing materials are made.
CN201710766093.2A 2017-08-30 2017-08-30 ZIF-8@ MG composite adsorption material for selectively adsorbing copper ions in wastewater Expired - Fee Related CN107376853B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108201878A (en) * 2018-02-08 2018-06-26 华南理工大学 The preparation method and water pollutant of a kind of carbon dots modified metal organic backbone sorbing material administer application
CN108854975A (en) * 2018-07-18 2018-11-23 西北农林科技大学 A kind of rodlike ZIF-8 material and its preparation method and application
CN110777537A (en) * 2019-11-04 2020-02-11 北京理工大学 ZIF-8/non-woven fabric composite material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498716A (en) * 2016-01-15 2016-04-20 辽宁石油化工大学 Waste paper fiber-based solid adsorption material and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498716A (en) * 2016-01-15 2016-04-20 辽宁石油化工大学 Waste paper fiber-based solid adsorption material and preparation method and application thereof

Non-Patent Citations (2)

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居静霞等: "碱处理棉纱载银工艺及其抗菌性研究", 《印染助剂》 *
王晨: "金属有机骨架/纸浆纤维复合材料的原位制备及抑菌性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108201878A (en) * 2018-02-08 2018-06-26 华南理工大学 The preparation method and water pollutant of a kind of carbon dots modified metal organic backbone sorbing material administer application
CN108854975A (en) * 2018-07-18 2018-11-23 西北农林科技大学 A kind of rodlike ZIF-8 material and its preparation method and application
CN110777537A (en) * 2019-11-04 2020-02-11 北京理工大学 ZIF-8/non-woven fabric composite material and preparation method thereof

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