CN105457614B - A kind of preparation method of the copper absorption agent based on metal-organic framework materials - Google Patents

A kind of preparation method of the copper absorption agent based on metal-organic framework materials Download PDF

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CN105457614B
CN105457614B CN201510817325.3A CN201510817325A CN105457614B CN 105457614 B CN105457614 B CN 105457614B CN 201510817325 A CN201510817325 A CN 201510817325A CN 105457614 B CN105457614 B CN 105457614B
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organic framework
dmf
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CN105457614A (en
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王洋
叶桂琴
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Yangzhou University
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Yangzhou 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]
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • 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
    • 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)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A kind of preparation method of the copper absorption agent based on metal-organic framework materials of the present invention, a kind of Inorganic-organic Hybrid Material for Treatment of Copper waste water and preparation method thereof is disclosed, the Inorganic-organic Hybrid Material adsorbent is prepared by metal organic framework by the method for rear synthetic modification.Compared with other sorbing materials, the hybrid material has high-adsorption-capacity (42.70mg/g), the hybrid material of the present invention is using sulfydryl as adsorption site simultaneously, therefore the speed of adsorbing metal ions is faster (15min), and copper ion can be efficiently separated.In addition, the adsorbent also has the characteristics of stability is good, it may be reused at least 30 times, reduce use cost.

Description

A kind of preparation method of the copper absorption agent based on metal-organic framework materials
Technical field
The present invention relates to technical field of waste water processing, and in particular to a kind of copper-containing wastewater adsorbent and preparation method thereof.
Background technology
Copper is the essential trace element in organism, has material impact for nerve system of human body and immune system etc., But when the too high levels of the copper in human body, the internal organs in body can be caused to bear when concentration is more than 1.3ppm, maintain human body Interior metabolism will get muddled, hepatic sclerosis, and liver ascites is even even more serious.
The method of conventional processing heavy metal copper has many kinds, such as chemical precipitation method, oxidation-reduction method, Coagulation Method, ion Exchange process and biological treatment etc..But these processing methods are limited by each side, secondary pollution be present, effect is paid no attention to The shortcomings of thinking, and being unfavorable for operation, so as to limit its application in heavy metals removal.
Absorption method due to its energy consumption is low, regenerating easily, easily operation the advantages that cause the concern of lot of domestic and international scholar.Mesh Before, people mainly use zeolite, silicon, organic adsorbent and activated carbon to adsorb the heavy metal ion in waste water as adsorbent, but These adsorbent adsorption capacities are low, time length.
The content of the invention
In view of the above-mentioned problems, the present invention proposes a kind of preparation side of Inorganic-organic Hybrid Material for Treatment of Copper waste water Method, can have the inorganic organic hybrid sorbents of efficient removal effect, the nothing with a kind of synthetically prepared heavy metal copper ion Machine organic Hybrid Materials property is stable, and absorption property is excellent.
To achieve the above object, the present invention provides following technical scheme：
A kind of preparation method of the copper absorption agent based on metal-organic framework materials, its preparation process are as follows：
(1)H2TCPP synthesis：Pyrroles and p formylbenzoic acid methyl esters are dissolved in propionic acid, by mixed solution in darkroom Under the conditions of back flow reaction, be cooled to room temperature after reaction, reaction product be dissolved in solvent, add KOH solution mixing, stirring is anti- Should, room temperature is cooled to after reaction, solvent is evaporated, water is added until solid is completely dissolved, adds hydrochloric acid solution to not regenerating Precipitation, is washed with water, and dries；
(2) MMPF-6 synthesis：Zirconium oxychloride is dissolved in DMF, ultrasonic dissolution, adds the product that step (1) obtains, surpassed Sonication, add benzoic acid and being transferred in stainless steel cauldron and reacted, room temperature is cooled to after reaction, successively with DMF and Acetone washs, and dries.
(3) MMPF-6 activation：The product that step (2) obtains is dissolved in DMF and HCl mixed solution, and is transferred to Reacted in stainless steel cauldron, cooled down after reaction；Supernatant liquor is poured out, is washed with DMF and acetone, is filtered, vacuum drying；
(4) MMPF-6's is mercapto-functionalized：The product that step (3) obtains is added in stainless steel cauldron, adds mercapto Guanidine-acetic acid and DMF solution, heated sealed reaction, filtering, soaked with fresh hot DMF, washed successively with DMF, acetone and ether.
Wherein, the solvent described in step (1) is the mixed solution of tetrahydrofuran and methanol.
Wherein, step (2), (3), stainless steel cauldron is with the stainless of teflon lined used in (4) Steel reactor.
Wherein, the reaction condition in step (2) in a kettle is to react 72h at 130 DEG C；Dried strip in step (2) Part is that 48h is dried at 120 DEG C.
Wherein, 50 DEG C are cooled to after being reacted in a kettle in step (3)
Wherein, the reaction condition in step (3) in a kettle is the heating response 24h at 100 DEG C, true in step (3) The condition of sky drying is in 120 DEG C of vacuum drying 12h.
Wherein, the reaction condition in step (4) in a kettle is that 60 DEG C of heated sealeds react 24h.
MMPF-6 specific surface areas prepared by the step (3) are 2188m2/ g, pore volume 1.309cm3/g。
MMPF-6 specific surface areas prepared by the step (4) are 1436m2/ g, pore volume 0.9036cm3/g。
The present invention has advantages below：
The laboratory clearance of heavy metal copper ion adsorbent prepared by the present invention reaches more than 85%.The absorption of the present invention Agent may be reused 30 times, and saturated adsorption capacity is big (42.70mg/g), and adsorption efficiency is high, and it is flat can to reach within 15 minutes absorption Weighing apparatus.The adsorbent can also also have notable adsorption effect, and alkali common in water sample gold to other contents of many kinds of heavy metal ion Category and alkaline-earth metal do not compete copper absorption interference.
Brief description of the drawings
Fig. 1 is the ESEM of metal-organic framework materials adsorbent mercapto-functionalized described in the embodiment of the present invention 1 Figure；
Fig. 2 is the X ray photoelectricity of metal-organic framework materials adsorbent mercapto-functionalized described in the embodiment of the present invention 1 Sub- energy spectrum diagram；
Fig. 3 is the repeatable profit of metal-organic framework materials adsorbent mercapto-functionalized described in the embodiment of the present invention 1 The property used.
Embodiment
With reference to specific embodiment, the invention will be further described.
The preparation method of copper absorption agent of the embodiment 1 based on metal-organic framework materials
(1) pyrroles and p formylbenzoic acid methyl esters are dissolved in propionic acid, solution flowed back 12h under dark room conditions, instead Mixture is answered to be cooled to room temperature.Product is dissolved in the mixed solution of tetrahydrofuran and methanol, is added KOH solution and is mixed 12h, room temperature is cooled to, tetrahydrofuran and methanol are evaporated, add water until solid is completely dissolved, addition hydrochloric acid solution is to no longer Generation precipitation, is washed with water, and dries.
(2) zirconium oxychloride is dissolved in ultrasonic dissolution in DMF, adds the product ultrasound 10min that step (1) obtains, add benzene Formic acid is simultaneously transferred in the reactor of polytetrafluoroethyllining lining 72h at 130 DEG C.After reactant is cooled to room temperature, successively with DMF and Acetone is washed, and 48h is dried at 120 DEG C.
(3) product that step (2) obtains is dissolved in DMF and HCl, and is transferred to the stainless steel with teflon lined In reactor, 24h is heated at 100 DEG C, is cooled to 50 DEG C.Supernatant liquor is poured out, is washed with DMF and acetone, is filtered, 120 DEG C vacuum drying 12h.
(4) product that step (3) obtains is added in the stainless steel cauldron with teflon lined, adds mercapto Guanidine-acetic acid and DMF solution, 60 DEG C of heated sealed 24h, filtering, soaked with fresh hot DMF, with DMF, acetone, ether washs successively, Mercapto-functionalized metal-organic framework materials adsorbent is prepared.
The result of the test of embodiment 2 determines
The mercapto-functionalized metal-organic framework materials adsorbent that embodiment 1 is prepared carries out polluted by copper experiment. 100mL waste water is taken into beaker, 10mg Absorbents are added into waste water, with NaOH or HNO3PH value of solution is adjusted to 5, room temperature After lower concussion absorption 15min, supernatant is taken, remaining copper ion concentration in clear liquid is detected by flame atomic absorption spectrometry.Weight Clearance w=(concentration after initial concentration-absorption)/initial concentration of metal ion, testing result are as shown in table 1.
Table 1
Initial concentration (mg/L) Concentration (mg/L) after absorption
Sample 1 10 5.84
Sample 2 9.0 4.90
Sample 3 8.0 3.73
Sample 4 7.0 2.74
Sample 5 6.0 1.8
As shown in Table 1, Absorbent provided by the invention has excellent absorption to the heavy metal copper ion in waste water Property, adsorption efficiency is more than 95%.This is attributed to the bigger serface of metal-organic framework materials and the strong characterization of adsorption of sulfydryl, makes Obtaining obtained Absorbent has excellent absorption property.
The mercapto-functionalized metal-organic framework materials adsorbent that embodiment 1 is prepared is to the copper absorption in water Capacity is big, recycles often, adsorption efficiency is fast, is easy to separate with the aqueous solution, it is convenient to omit the operation of solid-liquid centrifugation separation Step, realize easily and efficiently adsorption operations.It is new using providing for the actual absorption removal of heavy metal in waste water copper ion Approach.
It is described above, only it is presently preferred embodiments of the present invention, any formal limitation not is made to the present invention, it is any ripe Professional and technical personnel is known, it is without departing from the scope of the present invention, real to more than according to the technical spirit of the present invention Apply any simple modification, equivalent substitution that example made and improve etc., still fall within technical solution of the present invention protection domain it It is interior.

Claims (6)

  1. A kind of 1. preparation method of the copper absorption agent based on metal-organic framework materials, it is characterised in that：Preparation process is such as Under：
    (1)H2TCPP synthesis：Pyrroles and p formylbenzoic acid methyl esters are dissolved in propionic acid, by mixed solution in dark room conditions Lower back flow reaction, is cooled to room temperature after reaction, reaction product is dissolved in solvent, adds KOH solution and mixes, stirring reaction, Room temperature is cooled to after reaction, solvent is evaporated, adds water until solid is completely dissolved, addition hydrochloric acid solution is heavy to not regenerating Form sediment, be washed with water, dry；
    (2) MMPF-6 synthesis：Zirconium oxychloride is dissolved in DMF, ultrasonic dissolution, the product that addition step (1) obtains, at ultrasound Reason, add benzoic acid and be transferred in stainless steel cauldron and reacted, room temperature is cooled to after reaction, successively with DMF and acetone Washing, dry；
    (3) MMPF-6 activation：The product that step (2) obtains is dissolved in DMF and HCl mixed solution, and is transferred to stainless Reacted in steel reactor, cooled down after reaction；Supernatant liquor is poured out, is washed with DMF and acetone, is filtered, vacuum drying；
    (4) MMPF-6's is mercapto-functionalized：The product that step (3) obtains is added in stainless steel cauldron, adds sulfydryl second Acid and DMF solution, heated sealed reaction, filtering, soaked with fresh hot DMF, washed successively with DMF, acetone and ether；
    Reaction condition in step (3) in a kettle is the heating response 24h at 100 DEG C, the bar of vacuum drying in step (3) Part is in 120 DEG C of vacuum drying 12h；
    50 DEG C are cooled to after being reacted in a kettle in step (3)；
    Reaction condition in step (4) in a kettle reacts 24h for 60 DEG C of heated sealeds.
  2. 2. the preparation method of the copper absorption agent based on metal-organic framework materials, its feature exist as claimed in claim 1 In：Solvent described in step (1) is the mixed solution of tetrahydrofuran and methanol.
  3. 3. the preparation method of the copper absorption agent based on metal-organic framework materials, its feature exist as claimed in claim 1 In：Step (2), (3), stainless steel cauldron is the stainless steel cauldron with teflon lined used in (4).
  4. 4. the preparation method of the copper absorption agent based on metal-organic framework materials, its feature exist as claimed in claim 1 In：Reaction condition in step (2) in a kettle is to react 72h at 130 DEG C；Drying condition is at 120 DEG C in step (2) Dry 48h.
  5. 5. the preparation method of the copper absorption agent based on metal-organic framework materials, its feature exist as claimed in claim 1 In：MMPF-6 specific surface areas prepared by the step (3) are 2188m2/ g, pore volume 1.309cm3/g。
  6. 6. the preparation method of the copper absorption agent based on metal-organic framework materials, its feature exist as claimed in claim 1 In：MMPF-6 specific surface areas prepared by the step (4) are 1436m2/ g, pore volume 0.9036cm3/g。
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CN105817204A (en) * 2016-04-22 2016-08-03 宁波高新区夏远科技有限公司 Heavy metal ion adsorption film and preparation method thereof
CN106588951B (en) * 2017-01-23 2019-01-01 辽宁大学 A kind of porous metal-organic framework compound and its preparation method and application based on zinc
CN113293621B (en) * 2021-04-23 2022-09-16 中交天津港湾工程研究院有限公司 Preparation method of hydrophobic thiolated Zr-MOFs modified non-woven fabric, prepared modified non-woven fabric and application thereof

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