CN109046257A - It is a kind of for adsorbing the FeCl of fluorine ion3The preparation method and applications of modified ZIF-8 compound adsorbent - Google Patents

It is a kind of for adsorbing the FeCl of fluorine ion3The preparation method and applications of modified ZIF-8 compound adsorbent Download PDF

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Publication number
CN109046257A
CN109046257A CN201811006840.3A CN201811006840A CN109046257A CN 109046257 A CN109046257 A CN 109046257A CN 201811006840 A CN201811006840 A CN 201811006840A CN 109046257 A CN109046257 A CN 109046257A
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China
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fecl
zif
compound adsorbent
adsorbing
preparation
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CN201811006840.3A
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Chinese (zh)
Inventor
王治科
朱韵怡
张柏爽
王全坤
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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/027—Compounds of F, Cl, Br, I
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds

Abstract

The invention discloses a kind of for adsorbing the FeCl of fluorine ion3The preparation method and applications of modified ZIF-8 compound adsorbent, belong to the preparation technical field of fluoride waste adsorbent.Technical solution of the present invention main points are as follows: by 86.5mg FeCl3·6H2O is scattered in 15mL methanol, and 100mg ZIF-8 is added under stirring conditions in 40 DEG C, is reacted 30min, then be centrifuged 10min with the revolving speed of 6000rmp, is then obtained the FeCl for adsorbing fluorine ion in 50 DEG C of vacuum drying 12h3Modified ZIF-8 compound adsorbent, the compound adsorbent can be used in handling fluoride waste.Preparation process of the present invention is simple, reaction condition is mild and synthesis cycle is shorter, and the compound adsorbent large amount of adsorption of synthesis, the rate of adsorption is fast, and fluoride ion removing adsorption rate reaches 75% or more when for handling fluoride waste.

Description

It is a kind of for adsorbing the FeCl of fluorine ion3The preparation side of modified ZIF-8 compound adsorbent Method and its application
Technical field
The invention belongs to the preparation technical fields of fluoride waste adsorbent, and in particular to a kind of for adsorbing fluorine ion FeCl3The preparation method and applications of modified ZIF-8 compound adsorbent.
Background technique
If the fluorine of people's excess intake can be poisoned, the eubolism of calcium, phosphorus will affect, inhibit the activity of enzyme, influence endocrine The function of gland.Many water bodys all detect that fluorine content is exceeded, this is to cause the main approach that fluorine content is excessively high in animal and plant body One of.The method for removing Natural zeolite of fluorinated water includes coagulant sedimentation, ion-exchange, absorption method etc..
ZIF-8 has unique advantage, ZIF-8 and its modified composite material quilt as one of metal-organic framework materials The various pollutants being widely used in Adsorption water, but ZIF-8 does not have Adsorption ability to fluorine ion.Therefore, to ZIF-8 It is modified to improve it to the adsorption capacity of fluorine and obtain extensive concern.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of for adsorbing the FeCl of fluorine ion3The modified compound suction of ZIF-8 Attached dose of preparation method, the compound adsorbent is fast to the Adsorption rate of fluorine ion and large amount of adsorption, common coexisting ion pair Compound adsorbent absorption fluorine ion has little effect, therefore the compound adsorbent can be used in handling fluoride waste.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of for adsorbing the FeCl of fluorine ion3Change The preparation method of property ZIF-8 compound adsorbent, it is characterised in that specific steps are as follows: by 86.5mg FeCl3·6H2O is scattered in In 15mL methanol, in 40 DEG C under stirring conditions be added 100mg ZIF-8, react 30min, then with the revolving speed of 6000rmp from Then heart 10min obtains the FeCl for adsorbing fluorine ion in 50 DEG C of vacuum drying 12h3Modified ZIF-8 compound adsorbent.
The FeCl of the present invention for being used to adsorb fluorine ion3Modified ZIF-8 compound adsorbent is in processing fluoride waste Application, the removal adsorption rate of fluorine ion reaches 75% or more.
Preparation process of the present invention is simple, reaction condition is mild and synthesis cycle is shorter, the compound adsorbent adsorbance of synthesis Greatly, the rate of adsorption is fast, and fluoride ion removing adsorption rate reaches 75% or more when for handling fluoride waste.
Detailed description of the invention
Fig. 1 is ZIF-8 and ZIF-8 (FeCl3) infrared spectrum；
Fig. 2 is ZIF-8 and ZIF-8 (FeCl3) XRD spectra；
Fig. 3 is ZIF-8 (FeCl3) curve of adsorption kinetics；
ZIF-8 (FeCl when Fig. 4 is fluorine ion initial concentration difference3) the adsorption effect figure；
Fig. 5 is the initial pH of solution to ZIF-8 (FeCl3) absorption influence diagram；
Fig. 6 is common coexisting ion to ZIF-8 (FeCl3) absorption influence diagram.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Embodiment
Prepare ZIF-8 (FeCl3)
The preparation of compound adsorbent is to utilize conventional method synthesis ZIF-8 spare first, then uses FeCl3ZIF-8 is changed Property.
Synthesis ZIF-8: 1.17g (3.93mmol) Zn (NO is weighed3)2·6H2O is dissolved in 8mL deionized water, is weighed 22.60g (275.3mmol) 2-methylimidazole is dissolved in 80mL deionized water, and zinc nitrate solution is poured into 2- under stirring condition In methyl imidazole solution, it is stirred to react 5min, then 20min is centrifuged with the revolving speed of 10000rmp, is washed 2-3 times with dehydrated alcohol, It is spare that ZIF-8 is obtained for 24 hours in 60 DEG C of vacuum drying.
Synthesize compound adsorbent: by 86.5mg FeCl3·6H2O is dissolved in 15mL methanol, in 40 DEG C of conditions in stirring Lower addition 100mg ZIF-8 reacts 30min, then is centrifuged 10min with the revolving speed of 6000rmp, then in 50 DEG C of vacuum drying 12h Obtain the FeCl for adsorbing fluorine ion3Modified ZIF-8 compound adsorbent, is labeled as ZIF-8 (FeCl3)。
Characterization
Fig. 1 is ZIF-8 and ZIF-8 (FeCl3) infrared spectrum.As seen from the figure, the infrared signature absorption peak of ZIF-8 is clear As it can be seen that ZIF-8 (FeCl3) there were significant differences with the infrared spectrum of ZIF-8, this shows ZIF-8 (FeCl3) successfully synthesize.
Fig. 2 is ZIF-8 and ZIF-8 (FeCl3) XRD spectra.As seen from the figure, the ZIF-8 (FeCl of synthesis3) without obvious special Levy peak.
Table 1 is ZIF-8 and ZIF-8 (FeCl3) BET analyze result.Seen from table 1, the adsorbent ZIF-8 of synthesis (FeCl3) compared with ZIF-8, specific surface area and pore volume substantially reduce.
Table 1ZIF-8 and ZIF-8 (FeCl3) BET analysis
Absorption property
Fig. 3 is ZIF-8 (FeCl3) curve of adsorption kinetics.Experiment condition: concentration be respectively 20mg/L, 30mg/L, The fluorine-containing solution 20mL of 40mg/L, adsorbent ZIF-8 (FeCl3) 10mg, 30 DEG C, when oscillation absorption is different under the conditions of 150rmp Between.As seen from the figure, quickly, when initial Funing tablet is 40mg/L, when time of contact 30min, reaches balance to the adsorbent rate of adsorption The 94.6% of adsorbance.
Fig. 4 is influence diagram of the fluorine ion initial concentration to absorption.Experiment condition: concentration be respectively 10mg/L, 20mg/L, The fluorine-containing solution 20mL of 30mg/L, 40mg/L, 50mg/L, 60mg/L, 80mg/L, 100mg/L, adsorbent ZIF-8 (FeCl3) 10mg, 30 DEG C, oscillation absorption 7h under the conditions of 150rmp.As seen from the figure, as the increase adsorbance of initial concentration increases therewith, when When initial concentration is 100mg/L, ZIF-8 (FeCl3) absorption of fluorine ion is tended to be saturated.
Fig. 5 is influence diagram of the pH value of solution to absorption.Experiment condition: 20mL concentration is to add 10mg in 20mg/L fluorine solution Adsorbent, at 30 DEG C, oscillation absorption 7h under the conditions of 150rmp.As seen from the figure, the pH of solution is significant to Adsorption Effect, molten after absorption The pH of liquid also has significant change, and when pH value of solution is 4, adsorbance is maximum.
Fig. 6 is influence of the common coexisting ion to absorption.Experiment condition are as follows: 20mL fluorinion concentration is the molten of 20mg/L Liquid, 10mg adsorbent, 30 DEG C, oscillation absorption 7h under the conditions of 150rmp, the concentration of common coexisting ion is 20mg/L.By scheming It is found that phosphate radical is most significant to Adsorption Effect.
The simulated water sample of fluoride ion is prepared with the mineral water of different location respectively, fluorine ion initial concentration is 20mg/L points It does not take 20mL simulated water sample to be added in 100mL conical flask, 10mg adsorbent ZIF-8 (FeCl is added3), 30 DEG C, 150rmp oscillation 7h.Table 2 it is found that fluorine ion adsorption rate 75% or more.
Table 2ZIF-8 (FeCl3) the Adsorption fluorine ion from simulated water sample
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. a kind of for adsorbing the FeCl of fluorine ion3The preparation method of modified ZIF-8 compound adsorbent, it is characterised in that specific step Suddenly are as follows: by 86.5mg FeCl3·6H2O is scattered in 15mL methanol, and 100mg ZIF-8 is added under stirring conditions in 40 DEG C, 30min is reacted, then 10min is centrifuged with the revolving speed of 6000rmp, is then obtained in 50 DEG C of vacuum drying 12h for adsorbing fluorine ion FeCl3Modified ZIF-8 compound adsorbent.
2. obtained for adsorbing the FeCl of fluorine ion according to the method for claim 13Modified ZIF-8 compound adsorbent exists The application in fluoride waste is handled, the removal adsorption rate of fluorine ion reaches 75% or more.
CN201811006840.3A 2018-08-31 2018-08-31 It is a kind of for adsorbing the FeCl of fluorine ion3The preparation method and applications of modified ZIF-8 compound adsorbent Pending CN109046257A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7138063B1 (en) * 2001-06-20 2006-11-21 Sandia Corporation Method of removing arsenic and other anionic contaminants from contaminated water using enhanced coagulation
CN101139143A (en) * 2007-08-14 2008-03-12 天津市华宇膜技术有限公司 Hyperfiltration reverse- rinsing water recovery processing method and device thereof
CN104096542A (en) * 2014-06-23 2014-10-15 广西师范大学 Novel magnetic Fe / C@ MOF composite absorbent and preparation method thereof
CN106975456A (en) * 2017-05-12 2017-07-25 中南大学 A kind of defluorination material, preparation and its application
CN107486164A (en) * 2017-08-30 2017-12-19 河南师范大学 A kind of preparation method of@FP composite adsorbing materials of ZIF 8 and its application in adsorption cleaning Treatment of Copper waste water

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7138063B1 (en) * 2001-06-20 2006-11-21 Sandia Corporation Method of removing arsenic and other anionic contaminants from contaminated water using enhanced coagulation
CN101139143A (en) * 2007-08-14 2008-03-12 天津市华宇膜技术有限公司 Hyperfiltration reverse- rinsing water recovery processing method and device thereof
CN104096542A (en) * 2014-06-23 2014-10-15 广西师范大学 Novel magnetic Fe / C@ MOF composite absorbent and preparation method thereof
CN106975456A (en) * 2017-05-12 2017-07-25 中南大学 A kind of defluorination material, preparation and its application
CN107486164A (en) * 2017-08-30 2017-12-19 河南师范大学 A kind of preparation method of@FP composite adsorbing materials of ZIF 8 and its application in adsorption cleaning Treatment of Copper waste water

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