CN107486165A - A kind of preparation method of@FP composite adsorbing materials of ZIF 67 and its application in separation and concentration high-salt wastewater containing cadmium - Google Patents

A kind of preparation method of@FP composite adsorbing materials of ZIF 67 and its application in separation and concentration high-salt wastewater containing cadmium Download PDF

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Publication number
CN107486165A
CN107486165A CN201710765764.3A CN201710765764A CN107486165A CN 107486165 A CN107486165 A CN 107486165A CN 201710765764 A CN201710765764 A CN 201710765764A CN 107486165 A CN107486165 A CN 107486165A
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zif
composite adsorbing
adsorbing materials
solution
cadmium
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CN201710765764.3A
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CN107486165B (en
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王治科
陈海天
朱韵怡
叶存玲
范顺利
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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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

Abstract

The invention discloses a kind of preparation method of@FP composite adsorbing materials of ZIF 67 and its application in separation and concentration high-salt wastewater containing cadmium, specifically disclosing the preparation method of the@FP composite adsorbing materials of ZIF 67 includes ZIF 67 preparation and the preparation of the@FP composite adsorbing materials of ZIF 67, also discloses obtained application of the@FP composite adsorbing materials of ZIF 67 in separation and concentration high-salt wastewater containing cadmium.The present invention prepares the method mild condition of the@FP composite adsorbing materials of ZIF 67 and is easily controlled, the obtained@FP composite adsorbing material rates of adsorption of ZIF 67 are fast, strong antijamming capability, effectively cadmium can be adsorbed from high-salt wastewater, thiourea solution elution through 0.1mol/L after absorption, remain to keep higher absorption property to cadmium after 5 reuses, therefore, the cadmium ion that the@FP composite adsorbing materials of ZIF 67 can be used in separation and concentration high-salt wastewater containing cadmium as dispersive solid-phase extraction agent.

Description

A kind of preparation method of ZIF-67@FP composite adsorbing materials and its contain in separation and concentration Application in cadmium high-salt wastewater
Technical field
Separation and concentration technology field the invention belongs to the synthesis of composite adsorbing material and its for cadmium wastewater, is specifically related to And preparation method and its application in separation and concentration high-salt wastewater containing cadmium of a kind of ZIF-67@FP composite adsorbing materials.
Background technology
Cadmium and mercury, lead, chromium, arsenic are the five poisonous creatures: scorpion, viper, centipede, house lizard, toad in heavy metal.It is exactly that heavy metal chromium draws such as " Itai-itai diseases " that last century is broken out The whole body bone severe pain risen.The industry discharge such as battery, plating, alloy and metal mine exploitation, non-ferrous metal metallurgy is substantial amounts of Cadmium wastewater.Cadmium has been listed in one of toxicologic index of one of priority research pollutant and drinking water.Therefore, from water sample Separation and concentration cadmium has very important significance.
ZIF-67 is a kind of typical zeolite imidazole skeleton class material, and it has shown well to heavy metal ions in wastewater Absorption property, but zeolite imidazole metalloid organic framework compounds stability difference and repeatable usability is difficult, be unfavorable for from Separated in aqueous phase.It is of the invention by filter paper in order to overcome this problem（Filter Paper, FP）As metal organic framework ZIF- 67 carrier, ZIF-67 is stably immobilized on filter paper and maintaining its original absorption property.
The content of the invention
Present invention solves the technical problem that there is provided a kind of ZIF-67@FP composite adsorbing materials preparation method and its Application in separation and concentration high-salt wastewater containing cadmium, carrier of this method using filter paper as metal organic framework ZIF-67, by ZIF- 67 is stably immobilized on filter paper and its original absorption property is maintained, and the ZIF-67@FP composite adsorbing materials can conduct The cadmium ion that dispersive solid-phase extraction agent is used in separation and concentration high-salt wastewater containing cadmium.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of ZIF-67@FP composite adsorbing materials Preparation method, it is characterised in that concretely comprise the following steps：By 0.36g Co (NO3)2·6H2O, which is dissolved in 50mL deionized waters, obtains solution A, 1.32g 2-methylimidazoles are dissolved in 50mL deionized waters and obtain solution B, then Co will be contained2+Solution be added to solution B In obtain solution C, then solution A and solution C are mixed and 3h are stirred at room temperature ZIF-67 suspension is made；Cut 1cm*4cm Filter paper be placed in deionized water and soak 24h, then filter paper is added in ZIF-67 suspension, is subsequently placed in constant temperature oscillator 12h is vibrated under conditions of 25 DEG C, 120rpm, then stands 12h, is rinsed repeatedly with deionized water after taking-up, dries and ZIF- is made 67@FP composite adsorbing materials.
Application of the ZIF-67@FP composite adsorbing materials of the present invention in separation and concentration high-salt wastewater containing cadmium, it is special Sign is that detailed process is：Adsorption process, ZIF-67@FP composite adsorbing materials are added in high-salt wastewater containing cadmium, in 30 DEG C Vibration absorption 300min realizes the adsorption cleaning processing of the high-salt wastewater containing cadmium；Desorption process, the ZIF-67@FP after absorption is compound Sorbing material is added in the thiourea solution that molar concentration is 0.1mol/L, and after vibration desorption 24h, it is compound to take out ZIF-67@FP Sorbing material repetitive cycling after deionized water rinsing uses.
The present invention prepares the method mild condition of ZIF-67@FP composite adsorbing materials and is easily controlled, obtained ZIF-67@ The FP composite adsorbing material rates of adsorption are fast, strong antijamming capability, and cadmium can be effectively adsorbed from high-salt wastewater, is passed through after absorption 0.1mol/L thiourea solution elution, remains to keep higher absorption property, therefore, the ZIF-67@after 5 reuses to cadmium The cadmium ion that FP composite adsorbing materials can be used in separation and concentration high-salt wastewater containing cadmium as dispersive solid-phase extraction agent.
Brief description of the drawings
Fig. 1 is FP, ZIF-67 and ZIF-67@FP infrared spectrum；
Fig. 2 is FP, ZIF-67 and ZIF-67@FP XRD；
Fig. 3 is FP SEM figures；
Fig. 4 is ZIF-67 SEM figures；
Fig. 5 is ZIF-67@FP SEM figures；
Fig. 6 is the kinetic curve of ZIF-67@FP absorption cadmiums；
Fig. 7 is the influence curve that sodium chloride concentration adsorbs cadmium to ZIF-67@FP.
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-67@FP composite adsorbing materials：
ZIF-67 preparation
By 0.36g Co (NO3)2·6H2O, which is dissolved in 50mL deionized waters, obtains solution A, and 1.32g 2-methylimidazoles are dissolved in Solution B is obtained in 50mL deionized waters, then Co will be contained2+Solution be added in solution B and obtain solution C, then by solution A and Solution C, which mixes and 3h is stirred at room temperature, is made ZIF-67 suspension.
ZIF-67@FP preparation
Cutting 1cm*4cm filter paper, which is placed in deionized water, soaks 24h, then filter paper is added in ZIF-67 suspension, then It is placed in constant temperature oscillator under conditions of 25 DEG C, 120rpm and vibrates 12h, then stand 12h, is rushed repeatedly with deionized water after taking-up Wash, dry and ZIF-67@FP composite adsorbing materials are made.
2nd, characterize：
Fig. 1 is FP, ZIF-67 and ZIF-67@FP infrared spectrum.600-1500cm-1Absworption peak is being to belong to stretching for imidazole ring Contracting and flexural vibrations, 1584cm-1Absworption peak be due to 2929cm caused by the stretching vibration of C=N keys on imidazole ring-1Place Absworption peak be due on 2-methylimidazole caused by the stretching vibration of aromatic rings.The principal character absworption peak of filter paper exists 2118cm-1And 1109cm-1Locate, can significantly be observed in the infared spectrum of the ZIF-67@FP composite adsorbing materials of synthesis ZIF-67 characteristic absorption peak and the characteristic absorption peak of filter paper.
By to ZIF-67, FP and ZIF-67@FP carry out XRD tests, as shown in Fig. 2 ZIF-67 characteristic absorption peak and The characteristic absorption peak of filter paper can be observed on composite ZIF-67@FP, further demonstrate that ZIF-67 successes are immobilized Arrive on filter paper.
Compare ZIF-67, FP and ZIF-67@FP shape characteristic（As in Figure 3-5）, it can be clearly seen that filter paper is anti- Should front and rear pattern there occurs significant change, block ZIF-67 to have loaded on filter paper.
3rd, absorption property：
Fig. 6 is the kinetic curve of ZIF-67@FP absorption cadmiums.The ZIF-67@FP composite adsorbing materials are fast to the rate of adsorption of cadmium, 10min is adsorbed, when cadmium initial concentration is respectively 20mg/L and 50mg/L, adsorbance has respectively reached the 61.7% of maximal absorptive capacity With 83.9%.Experiment condition：Cadmium initial concentration is respectively 20mg/L and 50mg/L, volume 50mL, ZIF-67@FP composite adsorptions Material 80mg, 30 DEG C of temperature, oscillation rate 160rpm.
Fig. 7 is the influence curve that sodium chloride concentration adsorbs cadmium to ZIF-67@FP.As shown in Figure 5, ZIF-67@FP can be in height Under salt concentration conditions, effective absorption to cadmium is kept.Experiment condition：Cadmium initial concentration is 50mg/L, volume 50mL, ZIF- 67@FP composite adsorbing material 80mg, 30 DEG C, oscillation rate 160rpm, adsorption time 300min of temperature.
Table 1 is the influence that other coexistent metallic ions adsorb cadmium to ZIF-67@FP.As seen from table：In common metal ion Under conditions of coexisting, in addition to zinc ion and nickel ion, interference of other metal ions to cadmium sorption is smaller, ZIF-67@ FP remains to effectively adsorb to cadmium.Experiment condition is：Cadmium ion and other coexistent metallic ion concentration are 50mg/L, and volume is 50mL, ZIF-67@FP composite adsorbing material 80mg, 30 DEG C, oscillation rate 160rpm, time 300min of temperature.
The coexistent metallic ion of table 1 adsorbs the influence of cadmium to ZIF-67@FP
The regeneration cycle of ZIF-67@FP composite adsorbing materials uses
ZIF-67@FP after absorption cadmium are added in 0.1mol/L thiourea solution after vibration desorption 24h, take out ZIF-67@ FP is then added to through deionized water rinsing in the solution that cadmium initial concentration is 50mg/L, vibration absorption 300min, so repeats to inhale Attached-elution-sorption cycle 5 times again, ZIF-67@FP are followed successively by the adsorbance of cadmium：15.2mg/g、14.6mg/g、13.7mg/g、 13.0mg/g and 12.6mg/g, it is higher that this illustrates that the ZIF-67@FP composite adsorbing materials still have after 5 times are reused to cadmium Adsorption capacity.

Claims (2)

1. a kind of preparation method of ZIF-67@FP composite adsorbing materials, it is characterised in that concretely comprise the following steps：By 0.36g Co (NO3)2·6H2O, which is dissolved in 50mL deionized waters, obtains solution A, and 1.32g 2-methylimidazoles are dissolved in 50mL deionized waters and obtained To solution B, then Co will be contained2+Solution be added in solution B and obtain solution C, being then incorporated in room by solution A and solution C are mixed ZIF-67 suspension is made in temperature stirring 3h；Cutting 1cm*4cm filter paper, which is placed in deionized water, soaks 24h, then filter paper is added Into ZIF-67 suspension, it is subsequently placed in constant temperature oscillator under conditions of 25 DEG C, 120rpm and vibrates 12h, then stands 12h, Rinsed repeatedly with deionized water after taking-up, dry and ZIF-67 FP composite adsorbing materials are made.
2. ZIF-67@FP composite adsorbing materials give up in separation and concentration high salt containing cadmium made from the method according to claim 11 Application in water, it is characterised in that detailed process is：Adsorption process, ZIF-67@FP composite adsorbing materials are added to height containing cadmium In salt waste water, the adsorption cleaning processing of the high-salt wastewater containing cadmium is realized in 30 DEG C of vibration absorption 300min；Desorption process, after absorption ZIF-67@FP composite adsorbing materials be added to molar concentration be 0.1mol/L thiourea solution in, vibration desorption 24h after, take Go out ZIF-67@FP composite adsorbing materials repetitive cycling after deionized water rinsing to use.
CN201710765764.3A 2017-08-30 2017-08-30 Preparation method of ZIF-67@ FP composite adsorption material and application of adsorption material in separation and enrichment of cadmium-containing high-salt wastewater Expired - Fee Related CN107486165B (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN108854995A (en) * 2018-06-08 2018-11-23 河南师范大学 The preparation method and applications of HKUST-1@PMMA composite material of the one kind for adsorbing Pb (II)
CN108854994A (en) * 2018-06-08 2018-11-23 河南师范大学 The preparation method and applications of ZIF-67@PMMA composite material of the one kind for adsorbing Cd (II)
CN110665486A (en) * 2019-10-17 2020-01-10 福州大学 Magnetic ferroferric oxide-PAMAM-antibody complex and preparation method and application thereof
CN111321394A (en) * 2020-02-28 2020-06-23 盱眙新远光学科技有限公司 Method for preparing nano flaky cobalt phosphide by vapor deposition

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108854995A (en) * 2018-06-08 2018-11-23 河南师范大学 The preparation method and applications of HKUST-1@PMMA composite material of the one kind for adsorbing Pb (II)
CN108854994A (en) * 2018-06-08 2018-11-23 河南师范大学 The preparation method and applications of ZIF-67@PMMA composite material of the one kind for adsorbing Cd (II)
CN110665486A (en) * 2019-10-17 2020-01-10 福州大学 Magnetic ferroferric oxide-PAMAM-antibody complex and preparation method and application thereof
CN110665486B (en) * 2019-10-17 2021-05-18 福州大学 Magnetic ferroferric oxide-PAMAM-antibody complex and preparation method and application thereof
CN111321394A (en) * 2020-02-28 2020-06-23 盱眙新远光学科技有限公司 Method for preparing nano flaky cobalt phosphide by vapor deposition

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