CN107486164A - A kind of preparation method of@FP composite adsorbing materials of ZIF 8 and its application in adsorption cleaning Treatment of Copper waste water - Google Patents

A kind of preparation method of@FP composite adsorbing materials of ZIF 8 and its application in adsorption cleaning Treatment of Copper waste water Download PDF

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Publication number
CN107486164A
CN107486164A CN201710764914.9A CN201710764914A CN107486164A CN 107486164 A CN107486164 A CN 107486164A CN 201710764914 A CN201710764914 A CN 201710764914A CN 107486164 A CN107486164 A CN 107486164A
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zif
filter paper
composite adsorbing
distilled water
adsorbing materials
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CN201710764914.9A
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CN107486164B (en
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王治科
朱韵怡
陈海天
叶存玲
范顺利
陈凌云
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Henan Normal University
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Henan Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid 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
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention discloses a kind of preparation method of@FP composite adsorbing materials of ZIF 8 and its application in adsorption cleaning Treatment of Copper waste water, the filter paper bar that filter paper is cut to 1cm*4cm is placed in the sodium hydroxide solution that mass concentration is 10%, 2h is vibrated under conditions of 30 DEG C, 120r/min, again with distilled water flushing to neutrality, it is standby to obtain pretreatment filter paper in 60 DEG C of drying；By 1.17g Zn (NO3)2·6H2O is dissolved in 8mL distilled water, add pretreatment filter paper immersion 20min, the methylimidazoles of 22.6g 2 are dissolved in 80mL distilled water and pour into 2 methyl imidazole solutions of formation in the solution of immersion filter paper, 24h is vibrated under conditions of 30 DEG C, 120r/min, stand 24h, cleaned again through distilled water, composite adsorbing material is made in 60 DEG C of drying, also discloses application of the composite adsorbing material in adsorption cleaning Treatment of Copper waste water.The preparation method technique of the composite adsorbing material of the present invention is simple and convenient to operate and mild condition, and obtained composite adsorbing material adsorptive selectivity is strong, strong antijamming capability, the rate of adsorption are fast and are easily isolated.

Description

A kind of preparation method of ZIF-8@FP composite adsorbing materials and its adsorption cleaning processing Application in copper-containing wastewater
Technical field
The invention belongs to compound adsorbent technical field, and in particular to a kind of preparation side of ZIF-8@FP composite adsorbing materials Method and its application in adsorption cleaning Treatment of Copper waste water.
Background technology
ZIF-8 is metal-organic framework materials, has good hydrothermal stability, the specific surface area of super large and adjustable hole The advantages that footpath, also there is the revolving door effect that can be adsorbed more than itself aperture macromolecular, have become sorbing material field Study hotspot.However, ZIF-8 as sorbing material there is adsorbent separation it is more difficult the problem of because ZIF-8 compared with Small, settling property is poor, in laboratory, is generally separated with supercentrifuge.ZIF-8 will be applied to actual wastewater treatment In, it is necessary first to solve the separation problem of adsorbent, the present invention is attempted ZIF-8 and filter paper（FP）It is compounded to form composite adsorption material Expect to solve existing technical problem during use.
The content of the invention
Present invention solves the technical problem that there is provided a kind of ZIF-8@FP composite adsorbing materials preparation method and its Application in adsorption cleaning Treatment of Copper waste water, the ZIF-8@FP composite adsorbing materials successfully solve that ZIF-8 conducts are used alone Exist during adsorbent and separate the problem of difficult, and there is good absorption property, the absorption choosing of ZIF-8@FP composite adsorbing materials Selecting property is strong, strong antijamming capability, the rate of adsorption are fast and are easily isolated, and is handled suitable for the adsorption cleaning of copper-containing wastewater.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of system of ZIF-8@FP composite adsorbing materials Preparation Method, it is characterised in that concretely comprise the following steps：The filter paper bar that filter paper is cut to 1cm*4cm is placed in mass concentration as 10% In sodium hydroxide solution, 2h is vibrated under conditions of 30 DEG C, 120r/min, then with distilled water flushing to neutrality, in 60 DEG C of drying It is standby to obtain pretreatment filter paper；By 1.17g Zn (NO3)2·6H2O is dissolved in 8mL distilled water, adds pretreatment filter paper immersion 20min, 22.6g 2-methylimidazoles are dissolved in 80mL distilled water and the 2-methylimidazole solution of formation is poured into immersion filter paper Solution in, vibrate 24h under conditions of 30 DEG C, 120r/min, stand 24h, then cleaned through distilled water, is made in 60 DEG C of drying ZIF-8@FP composite adsorbing materials.
Application of the ZIF-8@FP composite adsorbing materials of the present invention in adsorption cleaning Treatment of Copper waste water, its feature It is that detailed process is：ZIF-8@FP composite adsorbing materials are placed in and configuration metal ions Zn2+、Cd2+、Ni2+、Mn2+、Co2+、 Mg2+ And Cr6+In the copper-containing wastewater coexisted, 180min is adsorbed in 30 DEG C and realizes that copper-containing wastewater adsorption cleaning is handled.
The preparation method technique of the ZIF-8@FP composite adsorbing materials of the present invention is simple and convenient to operate and mild condition, system The ZIF-8@FP composite adsorbing materials adsorptive selectivity obtained is by force, strong antijamming capability, the rate of adsorption are fast and are easily isolated, and is applied to The adsorption cleaning processing of copper-containing wastewater.
Brief description of the drawings
Fig. 1 is ZIF-8 infrared spectrum；
Fig. 2 is FP infrared spectrum；
Fig. 3 is ZIF-8@FP infrared spectrum；
Fig. 4 is ZIF-8 XRD spectra；
Fig. 5 is FP XRD spectra；
Fig. 6 is ZIF-8@FP XRD spectra；
Fig. 7 is ZIF-8 SEM figures；
Fig. 8 is FP SEM figures；
Fig. 9 is ZIF-8@FP SEM figures；
Figure 10 is absorbing copper influence curve of the equilibration time to ZIF-8@FP；
Figure 11 is the block diagram of ZIF-8@FP adsorptive selectivity.
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
1st, the preparation of ZIF-8@FP composite adsorbing materials：
Pre-process the preparation of filter paper
By filter paper be cut to 1cm*4cm filter paper bar be placed in mass concentration be 10% sodium hydroxide solution in, in 30 DEG C, Vibrate 2h under conditions of 120r/min, then with distilled water flushing to neutrality, obtain pre-processing filter paper in 60 DEG C of drying standby.
ZIF-8@FP preparation
By 1.17g Zn (NO3)2·6H2O is dissolved in 8mL distilled water, pretreatment filter paper immersion 20min is added, by 22.6g 2- Methylimidazole is dissolved in 80mL distilled water and pours into the 2-methylimidazole solution of formation in the solution of immersion filter paper, in 30 DEG C, 24h is vibrated under conditions of 120r/min, stands 24h, then is cleaned through distilled water, ZIF-8@FP composite adsorptions are made in 60 DEG C of drying Material.In order to prove that ZIF-8 is successfully synthesized and is successfully bonded on filter paper, filter paper is being not put into and other conditions are constant In the case of synthesize ZIF-8.
2nd, characterize：
Fig. 1-3 is ZIF-8, FP and ZIF-8@FP infrared spectrum.ZIF-8 infrared spectrums are in 1580cm-1Occur imidazole ring C= N key stretching vibration peaks, in 421cm-1There are Zn-N key stretching vibration peaks in place, and this shows that ZIF-8 is successfully prepared.ZIF-8@FP are red Outer spectrogram is in addition to possessing the characteristic absorption peak of filter paper infrared spectrum, in 421cm-1Place observed Zn-N key stretching vibration peaks, This proves that ZIF-8@FP are successfully prepared.
Fig. 4-6 is ZIF-8, FP and ZIF-8@FP XRD spectra.ZIF-8@FP XRD spectra occurs corresponding with ZIF-8 Consistent characteristic diffraction peak, while also there is consistent characteristic diffraction peak corresponding with filter paper, this explanation ZIF-8@FP synthesis ZIF-8 crystal structure is not destroyed.
Fig. 7-9 is ZIF-8, FP and ZIF-8@FP scanning electron microscope (SEM) photograph.ZIF-8 distribution of particles than more uniform, filter paper and ZIF-8@FP varying topographies are larger, and this shows that ZIF-8@FP are successfully prepared.
3rd, absorption property：
Figure 10 is influence curve of the equilibration time to ZIF-8@FP absorbing coppers.Experiment condition：ZIF-8@FP composite adsorbing materials one , Cu2+Concentration 50 μ g/mL solution 50mL, hunting speed 160r/min, 30 DEG C of temperature.ZIF-8@FP composite adsorbing materials are to copper The adsorption rate of ion is larger, and 180min adsorbances reach more than the 90% of equilibrium adsorption capacity.
Figure 11 is the adsorptive selectivity block diagram of ZIF-8@FP composite adsorbing materials.Experiment condition：Adsorbent is ZIF-8@ FP composite adsorbing materials one are opened, and various concentration of metal ions are 50 μ g/mL, volume 50mL, equilibration time 8h, hunting speed 160r/min, 30 DEG C of temperature.In Cu2+、Au3+、Pb2+、Zn2+、Cd2+、Ni2+、Mn2+、Co2+、Mg2+And Cr6+Deng in metal ion, ZIF-8@FP composite adsorbing materials present stronger adsorptive selectivity, to Cu2+Adsorbance be far longer than to other metals Adsorbance.
When table 1 gives common metal ion and copper ion and coexisted, absorption of the ZIF-8@FP composite adsorbing materials to copper.Inhale Attached dose is that ZIF-8 FP composite adsorbing materials one are opened, each metal ion species and respectively with copper ion composition binary system, and concentration It is 50 μ g/mL, volume 50mL, equilibration time 8h, hunting speed 160r/min, 30 DEG C of temperature.In Zn2+、Cd2+、Ni2+、Mn2+、 Co2+、Mg2+And Cr6+Under conditions of being coexisted respectively with copper ion Deng metal ion, ZIF-8@FP composite adsorbing materials are to copper ion Adsorbance do not reduce significantly, while very low to the adsorbance of common metal, this explanation ZIF-8@FP composite adsorption material Material absorption copper ion strong anti-interference performance.
The interference free performance of the ZIF-8@FP absorbing coppers of table 1

Claims (2)

1. a kind of preparation method of ZIF-8@FP composite adsorbing materials, it is characterised in that concretely comprise the following steps：Filter paper is cut to 1cm*4cm filter paper bar is placed in the sodium hydroxide solution that mass concentration is 10%, is shaken under conditions of 30 DEG C, 120r/min Swing 2h, then with distilled water flushing to neutrality, obtain pre-processing filter paper in 60 DEG C of drying standby；By 1.17g Zn (NO3)2·6H2O It is dissolved in 8mL distilled water, adds pretreatment filter paper immersion 20min, 22.6g 2-methylimidazoles are dissolved in 80mL distilled water And pour into the 2-methylimidazole solution of formation in the solution of immersion filter paper, 24h is vibrated under conditions of 30 DEG C, 120r/min, 24h is stood, then is cleaned through distilled water, ZIF-8@FP composite adsorbing materials are made in 60 DEG C of drying.
2. ZIF-8@FP composite adsorbing materials made from the method according to claim 11 are in adsorption cleaning Treatment of Copper waste water In application, it is characterised in that detailed process is：ZIF-8@FP composite adsorbing materials are placed in and configuration metal ions Zn2+、Cd2+、Ni2 +、Mn2+、Co2+、 Mg2+And Cr6+In the copper-containing wastewater coexisted, adsorb 180min in 30 DEG C and realize at copper-containing wastewater adsorption cleaning Reason.
CN201710764914.9A 2017-08-30 2017-08-30 Preparation method of ZIF-8@ FP composite adsorption material and application of adsorption material in adsorption and purification treatment of copper-containing wastewater Expired - Fee Related CN107486164B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108589399A (en) * 2018-05-11 2018-09-28 陕西科技大学 One kind being based on cellulose base/ZIF-8 composite material and preparation methods
CN109046257A (en) * 2018-08-31 2018-12-21 河南师范大学 It is a kind of for adsorbing the FeCl of fluorine ion3The preparation method and applications of modified ZIF-8 compound adsorbent
CN109174018A (en) * 2018-10-26 2019-01-11 吉林大学 A kind of Hg(II) monoblock type adsorbent material and remove water in Hg(II) method
CN109731555A (en) * 2019-03-04 2019-05-10 长春工业大学 One kind being used for CO2The preparation method and application of the ZIF-8/ shaddock veneer composite material of absorption
CN114505057A (en) * 2021-12-31 2022-05-17 石家庄循环化工研究院 ZIF-8/67 composite crystal adsorbent, preparation method thereof and wastewater purification method

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108589399A (en) * 2018-05-11 2018-09-28 陕西科技大学 One kind being based on cellulose base/ZIF-8 composite material and preparation methods
CN109046257A (en) * 2018-08-31 2018-12-21 河南师范大学 It is a kind of for adsorbing the FeCl of fluorine ion3The preparation method and applications of modified ZIF-8 compound adsorbent
CN109174018A (en) * 2018-10-26 2019-01-11 吉林大学 A kind of Hg(II) monoblock type adsorbent material and remove water in Hg(II) method
CN109174018B (en) * 2018-10-26 2022-12-02 吉林大学 Hg (II) monolithic adsorption material and method for removing Hg (II) in water
CN109731555A (en) * 2019-03-04 2019-05-10 长春工业大学 One kind being used for CO2The preparation method and application of the ZIF-8/ shaddock veneer composite material of absorption
CN109731555B (en) * 2019-03-04 2022-03-25 长春工业大学 For CO2Preparation method and application of adsorbed ZIF-8/shaddock peel composite material
CN114505057A (en) * 2021-12-31 2022-05-17 石家庄循环化工研究院 ZIF-8/67 composite crystal adsorbent, preparation method thereof and wastewater purification method
CN114505057B (en) * 2021-12-31 2024-05-24 石家庄循环化工研究院 ZIF-8/67 composite crystal adsorbent, preparation method thereof and wastewater purification method

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