CN105817204A - Heavy metal ion adsorption film and preparation method thereof - Google Patents
Heavy metal ion adsorption film and preparation method thereof Download PDFInfo
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- CN105817204A CN105817204A CN201610273898.9A CN201610273898A CN105817204A CN 105817204 A CN105817204 A CN 105817204A CN 201610273898 A CN201610273898 A CN 201610273898A CN 105817204 A CN105817204 A CN 105817204A
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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]
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- 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
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- 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
Abstract
The invention relates to a heavy metal ion adsorption film and a preparation method thereof. The adsorption film is composed of a metal organic frame material, 2-mercapto benzimidazole, a modifier, a stabilizer, a solvent A and a solvent B. The 2-mercapto benzimidazole is fixedly carried on the metal organic frame material and is used for enhancing the adsorption capacity of the adsorption film for the heavy metal ion.
Description
Technical field
The present invention relates to a kind of water treatment field, specifically, be one be applicable to efficient absorption heavy metal in waste water from
Adsorbed film of son and preparation method thereof.
Background technology
Along with the fast development of industrial society, the heavy metal ion in environment increases day by day, mainly has Cr6+、U6+、Te3+、
Co3+、Se6+、Pu3+、Hg2+、Mn4+Deng.Heavy metal contaminants enters environment with the form of waste water,waste gas and industrial residue,
And enter earth's surface and groundwater environment through processes such as atmospheric sedimentation, rainwash and soil leachings, and then pollute drinkable water
Source.Investigating according to the study, Industrial " three Waste " and the chemical fertilizer of agricultural and pesticide are heavy metal main sources in environment.Heavy metal
Pollutant have the features such as high toxicity, difficult degradation, biological concentration, and it can pass through food chain, drink water, breathes or contact skin
Etc. approach enter human body, endanger human health, wherein, arsenic, chromium, cadmium and nickel four heavy metal species can increase the mankind suffer from pulmonary carcinoma,
The risk of the cancers such as skin carcinoma, alimentary tract cancer, breast carcinoma；Lead, cadmium, hydrargyrum and arsenic four heavy metal species can interfere with human body and swash
The metabolism of element, causes various cental system, reproductive system and cardiovascular disease；It addition, copper, manganese, although zinc etc. are
The necessary trace element of human body, but health also can be caused damage by Excess free enthalpy.Therefore, preparation is a kind of efficiently, environmental protection,
Cheap adsorbing material is particularly important.
In the patent of invention of Application No. CN201010533375.6, describe weight in a kind of effectively removal drinking water
Membrane adsorbent of metal ion and preparation method thereof, mainly with polymer and resin at dimethyl sulfoxide, oxolane equal solvent
In be blended and prepare membrane adsorbent, but membrane adsorbent homogeneity prepared by the method is poor and unstable.In Application No.
In the patent of invention of CN201310528926.3, describe a kind of for removing the hybrid film adsorbent of heavy metal ion in water
Preparation method, with under the effect of diluted acid, polyvinyl alcohol is prepared by sol-gal process with cross-linking agent, silane coupler
Hybrid film adsorbent, but membrane adsorbent not only adsorption capacity prepared by the method is less, and usual whole sol-gel
Process is the longest, furthermore inevitably there is a large amount of micropore in gel, and in dry run, these micropores can escape many
Gas and Organic substance, and produce contraction, destroy membrane structure.
Summary of the invention
Present invention is primarily targeted at a kind of heavy metal ion adsorbed film of offer and preparation method thereof, it is by improving gold
Belonging to organic framework materials, preparation is applicable to the composite membrane of Adsorption of Heavy Metal Ions, thus heavy metal ion has high selectivity
While, also there is high power capacity, the wide suitability and renewable usability.
For reaching object above, the technical solution used in the present invention is: a kind of heavy metal ion adsorbed film is organic by metal
Frame material, 2-mercaptobenzimidazole, modifying agent, stabilizer, solvent orange 2 A and solvent B composition so that 2-sulfydryl benzene
And imidazoles is immobilized in metal-organic framework material, for the adsorption capacity strengthening described adsorbed film heavy metal ion.
According to one embodiment of the invention, metal-organic framework material is 20～30 parts, and 2-mercaptobenzimidazole is 5～10
Part, modifying agent is 1～5 part, and stabilizer is 0～2 part, and solvent orange 2 A is 40～60 parts, and solvent B is 5～10 parts.
According to one embodiment of the invention, described solvent orange 2 A is selected from dimethylformamide, dimethyl acetylamide, N-methyl
One or more in ketopyrrolidine, dimethyl sulfoxide, described solvent B is selected from ethanol, acetone, ethyl acetate
Plant or multiple.
According to one embodiment of the invention, described solvent orange 2 A is dimethylformamide, and described solvent B is ethanol.
According to one embodiment of the invention, described modifying agent selected from dodecylbenzene sodium sulfonate, sodium cetanesulfonate,
One or more in sodium lauryl sulphate.
According to one embodiment of the invention, described stabilizer is phosphate buffered solution, and it is by disodium hydrogen phosphate and phosphoric acid
Sodium dihydrogen is formulated.
According to one embodiment of the invention, described modifying agent is sodium lauryl sulphate.
A kind of preparation method of heavy metal ion adsorbed film, it includes step:
The metal-organic framework material of corresponding weight portion is scattered in solvent orange 2 A by S100, adds modifying agent under stirring,
It is warmed up to 60 DEG C, continues stirring 1～5 hour, add stabilizer and form dispersion liquid；
2-mercaptobenzimidazole is dissolved in solvent B by S200, and gained solution adds in described dispersion liquid, continues at 60 DEG C
Continuous stirring 1～6 hour, obtains casting solution；
S300, by described casting solution filtering and standing deaeration 1～2 hours, is cast in glass plate, is placed in baking oven being dried；
And
S400 is 110～120 DEG C of heat treatments 1～after 5 hours through temperature, is placed in 2mol/L sulphuric acid process 10～24 little
Time, rinse till cleaning mixture is neutrality with water afterwards, wet film is placed at 50～60 DEG C vacuum drying and obtains immobilized
The metal-organic framework material composite membrane of 2-mercaptobenzimidazole, prepares described heavy metal ion adsorbed film.
According to one embodiment of the invention, metal-organic framework material and 2-mercaptobenzimidazole matter in described preparation method
Amount ratio is 4: 1, and solvent orange 2 A and solvent B mass ratio are 8: 1.
According to one embodiment of the invention, the synthesis of the metal-organic framework material of described step S100 includes step:
The ferric chloride hexahydrate of respective quality is dissolved in deionized water by S110, and stirring is fully dissolved, and adds equal benzene three
Formic acid, continues stirring 0.5 hour；
Above-mentioned solution is loaded autoclave 130 DEG C and reacts 72 hours by S120；And
S130 is cooled to room temperature after the solution reaction of step S120 terminates, and washes three times with hot water and methanol, and in boiling
Processing in methanol 12 hours, 150 DEG C are vacuum dried 12 hours, obtain metal-organic framework material.
The invention have the benefit that
1,2-mercaptobenzimidazole has multiple adsorption site and is able to Adsorption of Heavy Metal Ions, but 2-mercaptobenzimidazole
Adsorption capacity is less, and the specific surface area of metal-organic framework material is big, and active sites is less, it is impossible to active adsorption heavy metal from
Son, by by immobilized for 2-mercaptobenzimidazole in metal-organic framework material, expand described adsorbed film heavy metal ion
Adsorption surface area, promote to be immobilized on the absorption of 2-mercaptobenzimidazole heavy metal ion of channel surfaces, thus strengthen
The adsorption capacity of adsorbed film；
2, being hydrophobic organic due to 2-mercaptobenzimidazole, metal-organic framework material surface cannot directly be adsorbed thin
Water Organic substance, the unsaturated coordinating metal center being had by metal-organic framework material, modifying agent such as DBSA
Sodium is able to it modified, obtains the metal framework material of modification；The hydrophobic group of 2-mercaptobenzimidazole and modified metal
The hydrocarbon end on frame material surface interacts so that 2-mercaptobenzimidazole is immobilized in metal-organic framework material；With
Time, stabilizer can promote metal-organic framework material to organic attachment trend, thus in modifying agent and the auxiliary of stabilizer
Under promotion, metal-organic framework material is able to successfully immobilized 2-mercaptobenzimidazole.
Detailed description of the invention
Hereinafter describe and be used for disclosing the present invention so that those skilled in the art are capable of the present invention.Below describe in excellent
Select embodiment to be only used as citing, it may occur to persons skilled in the art that other obvious modification.
A kind of heavy metal ion adsorbed film by metal-organic framework material, 2-mercaptobenzimidazole, modifying agent, stabilizer,
Solvent orange 2 A and solvent B composition, by by immobilized for 2-mercaptobenzimidazole in metal-organic framework material, for improvement
The adsorption rate of metal-organic framework material heavy metal ion.
Described metal-organic framework material is that MIL-100, MIL represent Material of Institut Lavoisier, and it is
Assembled by Iron cluster and trimesic acid part.
Its material composition composition is calculated as by weight: metal-organic framework material is 20～30 parts, 2-mercaptobenzimidazole
Being 5～10 parts, modifying agent is 1～5 part, and stabilizer is 0～2 part, and solvent orange 2 A is 40～60 parts, and solvent B is 5～10 parts.
Described solvent orange 2 A is in dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide
One or more, one or more in ethanol, acetone, the ethyl acetate of described solvent B.
Preferably, described solvent orange 2 A is dimethylformamide, and described solvent B is ethanol.
Described modifying agent one in dodecylbenzene sodium sulfonate, sodium cetanesulfonate, sodium lauryl sulphate
Or multiple, it is preferable that described modifying agent is sodium lauryl sulphate.
Described stabilizer is phosphate buffered solution, and it is formulated by disodium hydrogen phosphate and sodium dihydrogen phosphate.
N, S in 2-mercaptobenzimidazole has the adsorption site of exposure, is able to metal ion with the form of coordinate bond
In conjunction with, adsorb contents of many kinds of heavy metal ion, meanwhile, 2-mercaptobenzimidazole not only has the N adsorption site of benzimidazole, also
Having the S adsorption site of sulfydryl, the adsorptivity of the S adsorptivity than N is higher, thus, it is preferable to 2-mercaptobenzimidazole is used for
Adsorption of Heavy Metal Ions.Thus, the 2-mercaptobenzimidazole containing N, S coordination atom is not only to Cu2+、Cr3+、Ni2+、
Pb2+、Hg2+Excellent adsorptivity is had etc. heavy metal ion, and to Ag+、Au3+、Pd2+Have higher Deng precious metal ion
Selectivity and adsorption capacity.
Owing to 2-mercaptobenzimidazole is hydrophobic organic, and the surface of metal-organic framework material cannot directly be adsorbed thin
Water Organic substance, the unsaturated coordinating metal center being had by metal-organic framework material, modifying agent such as DBSA
Sodium is able to it modified, obtains the metal framework material of modification.The hydrophobic group of 2-mercaptobenzimidazole and modified metal
The hydrocarbon end on frame material surface interacts so that 2-mercaptobenzimidazole is immobilized in metal-organic framework material.With
Time, stabilizer can promote metal-organic framework material to organic attachment trend, therefore, auxiliary at modifying agent and stabilizer
Helping under promotion, metal-organic framework material is able to successfully immobilized 2-mercaptobenzimidazole.
A kind of preparation method of heavy metal ion adsorbed film, it includes step:
The metal-organic framework material of corresponding weight portion is scattered in solvent orange 2 A by S100, adds modifying agent under stirring,
It is warmed up to 60 DEG C, continues stirring 1～5 hour, add stabilizer and form dispersion liquid；
2-mercaptobenzimidazole is dissolved in solvent B by S200, and gained solution adds in described dispersion liquid, continues at 60 DEG C
Continuous stirring 1～6 hour, obtains casting solution；
S300, by described casting solution filtering and standing deaeration 1～2 hours, is cast in glass plate, is placed in baking oven being dried；
And
S400 is 110～120 DEG C of heat treatments 1～after 5 hours through temperature, is placed in 2mol/L sulphuric acid process 10～24 little
Time, rinse till cleaning mixture is neutrality with water afterwards, wet film is placed at 50～60 DEG C vacuum drying and obtains immobilized
The metal-organic framework material composite membrane of 2-mercaptobenzimidazole, prepares described heavy metal ion adsorbed film.
Preferably, in described preparation method, metal-organic framework material and 2-mercaptobenzimidazole mass ratio are 4: 1.
Preferably, in described preparation method, solvent orange 2 A and solvent B mass ratio are 8: 1.
Wherein, the synthesis of the metal-organic framework material of described step S100 includes step:
The ferric chloride hexahydrate of respective quality is dissolved in deionized water by S110, and stirring is fully dissolved, and adds equal benzene three
Formic acid, continues stirring 0.5 hour；
Above-mentioned solution is loaded autoclave 130 DEG C and reacts 72 hours by S120；And
S130 is cooled to room temperature after the solution reaction of step S120 terminates, and washes three times with hot water and methanol, and in boiling
Processing in methanol 12 hours, 150 DEG C are vacuum dried 12 hours, obtain metal-organic framework material.
Wherein, the preparation of metal-organic framework material also can be prepared by microwave assisting method or mechanical mixing method.
Owing to single metal-organic framework material has the advantage that specific surface area is high, duct is abundant, its active sites simultaneously
Less, it is difficult to adsorbing metal ions, and 2-mercaptobenzimidazole has the adsorption site of multiple exposure, to Metal Ion Selective Electrode
Property high, absorbability is very strong, but, it has less adsorption capacity, the poor suitability and is difficult to recycle.Cause
And, utilize the special cage structure of metal-organic framework material to can be used for accommodating this characteristic of guest molecule, by modifying agent and
The auxiliary of stabilizer, is able to be immobilized in metal-organic framework material 2-mercaptobenzimidazole, and still can keep 2-mercapto
The high selectivity of base benzimidazole heavy metal ion and adsorptivity, meanwhile, the special construction of metal-organic framework material can rise
To " microenvironment effect " so that the time lengthening in adsorbed film duct of the liquid holdup containing heavy metal ion, expand institute
State the adsorption surface area of adsorbed film heavy metal ion, promote to be immobilized on the 2-mercaptobenzimidazole heavy metal of channel surfaces
The absorption of ion, thus strengthen the adsorption capacity of adsorbed film.
Due to the stability that metal-organic framework material is good, contribute to separating regeneration and use.
It is high that heavy metal ion adsorbed film prepared by the present invention has water permeability, and the absorption of heavy metal and cutoff performance are good,
Regeneration simplicity, effectively removes the heavy metal ion in water.Shown by test experiments, immobilized by 2-mercaptobenzimidazole
Big at the composite membrane water flux of metal-organic framework material, heavy metal ion is (such as Hg2+、Cu2+) selectivity is high, suction
Attached capacity is high and easily cleans and regenerates.
Ferric chloride hexahydrate used in the following embodiment of the present invention, trimesic acid, methanol, dimethylformamide,
The reagent such as sodium lauryl sulphate, 2-mercaptobenzimidazole, ethanol are both from the Shanghai Aladdin limited public affairs of biochemical technology share
Department.Acticarbon purchased from Wuxi City Chen Kai activated carbon company limited.
Embodiment one
(1) preparation of metal-organic framework material
The preparation of metal-organic framework material MIL-100, including step: 2.7g ferric chloride hexahydrate is dissolved in 50mL
In deionized water, stirring is fully dissolved, and adds 1.39g trimesic acid, continues stirring 0.5h.Finally by above-mentioned molten
Liquid loads autoclave 130 DEG C reaction 72h.Question response is cooled to room temperature after terminating, and washes three times with hot water and methanol, and in boiling
Methanol boils 12h, 150 DEG C of vacuum drying 12h, obtains metal-organic framework material.
(2) preparation of heavy metal ion adsorbed film
Weighing 30 parts of metal-organic framework material to be scattered in 60 parts of dimethylformamides, stirring is lower adds 3 part 12
Alkyl sodium sulfate, is warmed up to 60 DEG C, continues stirring 1h, adds 2 parts of phosphate buffer and forms dispersion liquid.By 5 parts
2-mercaptobenzimidazole is dissolved in 5 parts of ethanol, and gained solution adds in above-mentioned dispersion liquid, continues stirring 1h, obtain at 60 DEG C
Casting solution.Casting solution filtering and standing deaeration 1h, is cast on a glass by casting solution, is placed in baking oven being dried, then
After temperature is 110 DEG C of heat treatment 1h, it is placed in 2M sulphuric acid process 10h, afterwards with deionized water rinsing until washing
Till liquid is neutrality, wet film is placed at 60 DEG C the metal organic frame that vacuum drying has obtained 2-mercaptobenzimidazole immobilized
Material cladding film.Its conditional is metal-organic framework material and 2-mercaptobenzimidazole mass ratio is 6: 1, solvent orange 2 A with
Solvent B mass ratio is 12: 1.
(3) adsorbed film performance test
In removing water, the adsorption experiment of heavy metal ion is the Hg (NO at 0.05mol/L3)2With 0.03mol/L's
Cu(NO3)2Solution is carried out.Experimentation is as follows: weigh the above-mentioned heavy metal ion adsorbed film absorption prepared of 1g
Agent is placed in conical flask, then pipettes the Hg (NO of 0.05mol/L3)2It is soaked by solution 40mL, more jointly puts
In the calorstat of 25 DEG C, carry out static adsorption 24h, then with funnel, sample leached from conical flask, collect filtrate,
In filtrate, add a certain amount of sodium acetate and hac buffer regulation pH=3, then be added thereto to two (mass fractions
0.2%) xylenol orange indicator, being subsequently adding (mass fraction 20%) hexamethylenetetramine buffer solution to solution is purple
Redness, the hexamethylenetetramine buffer solution adding 3mL, drip with the EDTA standard solution of 0.1mol/L the most again
Determining to take off completely to solution aubergine, thus can calculate Hg2+Adsorbance.
Use same method and steps, weigh the above-mentioned adsorbed film prepared of 1g and be placed in conical flask, add 0.03
Cu (the NO of mol/L3)2It is soaked by solution 40mL, regulates with a certain amount of sodium acetate and hac buffer
PH=4, carries out adsorbing 24h, the most again with the Na of 0.05mol/L under 25 DEG C of temperature conditionss2S2O3Standard solution titrates
Cu in filtrate after absorption2+Concentration, thus can calculate Cu2+Adsorbance.In order to contrast composite membrane, business is lived
Property carbon adsorbent also for heavy metal ion performance test.The main performance index of adsorbed film adsorbent and acticarbon is shown in
Table 1.
Embodiment two
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 20 parts, and 2-mercaptobenzimidazole is 5 parts, and modifying agent sodium lauryl sulphate is 3
Part, stabilizer phosphate buffer is 2 parts, and solvent orange 2 A dimethylformamide is 60 parts, and solvent B ethanol is 5 parts.Wherein
Condition is metal-organic framework material and 2-mercaptobenzimidazole mass ratio is 4: 1, and solvent orange 2 A and solvent B mass ratio are 12:
1。
Embodiment three
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 30 parts, and 2-mercaptobenzimidazole is 10 parts, and modifying agent sodium lauryl sulphate is 3
Part, stabilizer phosphate buffer is 2 parts, and solvent orange 2 A dimethylformamide is 60 parts, and solvent B ethanol is 5 parts.Wherein
Condition is metal-organic framework material and 2-mercaptobenzimidazole mass ratio is 3: 1, and solvent orange 2 A and solvent B mass ratio are 12:
1。
Embodiment four
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 20 parts, and 2-mercaptobenzimidazole is 10 parts, and modifying agent sodium lauryl sulphate is 3
Part, stabilizer phosphate buffer is 2 parts, and solvent orange 2 A dimethylformamide is 60 parts, and solvent B ethanol is 5 parts.Wherein
Condition is metal-organic framework material and 2-mercaptobenzimidazole mass ratio is 2: 1, and solvent orange 2 A and solvent B mass ratio are 12:
1。
Embodiment five
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 20 parts, and 2-mercaptobenzimidazole is 5 parts, and modifying agent sodium lauryl sulphate is 3
Part, stabilizer phosphate buffer is 2 parts, and solvent orange 2 A dimethylformamide is 40 parts, and solvent B ethanol is 5 parts.Wherein
Condition is metal-organic framework material and 2-mercaptobenzimidazole mass ratio is 4: 1, and solvent orange 2 A and solvent B mass ratio are 8:
1。
Embodiment six
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 20 parts, and 2-mercaptobenzimidazole is 5 parts, and modifying agent sodium lauryl sulphate is 3
Part, stabilizer phosphate buffer is 2 parts, and solvent orange 2 A dimethylformamide is 60 parts, and solvent B ethanol is 10 parts.Its
Conditional is metal-organic framework material and 2-mercaptobenzimidazole mass ratio is 4: 1, and solvent orange 2 A with solvent B mass ratio is
6∶1。
Embodiment seven
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 20 parts, and 2-mercaptobenzimidazole is 5 parts, and modifying agent sodium lauryl sulphate is 3
Part, stabilizer phosphate buffer is 2 parts, and solvent orange 2 A dimethylformamide is 40 parts, and solvent B ethanol is 10 parts.Its
Conditional is metal-organic framework material and 2-mercaptobenzimidazole mass ratio is 4: 1, and solvent orange 2 A with solvent B mass ratio is
4∶1。
Embodiment eight
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 20 parts, and 2-mercaptobenzimidazole is 5 parts, and modifying agent dodecylbenzene sodium sulfonate is 2
Part, stabilizer phosphate buffer is 1 part, and solvent orange 2 A N-Methyl pyrrolidone is 40 parts, and solvent B ethyl acetate is 5
Part.Its conditional is metal-organic framework material and 2-mercaptobenzimidazole mass ratio is 4: 1, solvent orange 2 A and solvent B matter
Amount ratio is 8: 1.
Embodiment nine
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 20 parts, and benzimidazole is 5 parts, and modifying agent sodium lauryl sulphate is 3 parts, surely
Determining agent phosphate buffer is 2 parts, and solvent orange 2 A dimethylformamide is 40 parts, and solvent B ethanol is 5 parts.Its conditional is
Metal-organic framework material and benzimidazole mass ratio are 4: 1, and solvent orange 2 A and solvent B mass ratio are 8: 1.
Embodiment ten
Each composition weight portion composition as follows, its preparation method and adsorbed film performance test with embodiment 1, its main property
Index can be shown in Table 1.MIL-100 is 20 parts, and modifying agent sodium lauryl sulphate is 3 parts, stabilizer phosphate buffer
Being 2 parts, solvent orange 2 A dimethylformamide is 40 parts, does not has 2-mercaptobenzimidazole and solvent B, tests independent metal organic
The absorption property of frame material.
The performance test results of the made heavy metal ion adsorbed film of table 1 embodiment
From table 1, the commercial acticarbon of contrast, the made membrane adsorbent of the present invention has high heavy metal ion
Adsorbance, it is possible to the heavy metal ion in absorption and recycle-water.Knowable to embodiment 1～8, wherein optimal condition
It is 4: 1 for metal-organic framework material and-mercaptobenzimidazole mass ratio, when solvent orange 2 A and solvent B mass ratio are 8: 1
Made adsorbed film can obtain the highest adsorbance.
Knowable to embodiment 9, not only there is due to 2-mercaptobenzimidazole the N adsorption site of benzimidazole, also there is mercapto
The S adsorption site of base, the adsorptivity of the S adsorptivity than N is higher, thus, 2-mercaptobenzimidazole be better than benzimidazole for
Adsorption of Heavy Metal Ions.
Knowable to embodiment 10, owing to single metal-organic framework material active sites is less, it is difficult to adsorbing metal ions,
Needing could active adsorption heavy metal ion by the immobilized of 2-mercaptobenzimidazole.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technology of the industry
The personnel simply present invention it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description
Principle, the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, these change and
Improvement both falls within the range of claimed invention.The protection domain of application claims by appending claims and
Equivalent defines.
Claims (10)
1. a heavy metal ion adsorbed film, it is characterised in that described adsorbed film is by metal-organic framework material, 2-sulfydryl
Benzimidazole, modifying agent, stabilizer, solvent orange 2 A and solvent B composition so that 2-mercaptobenzimidazole is immobilized to be had in metal
Machine frame material.
Heavy metal ion adsorbed film the most according to claim 1, it is characterised in that described adsorbed film constitutive material
Weight portion is: 20～30 parts of metal-organic framework material, 5～10 parts of 2-mercaptobenzimidazoles, 1～5 part of modifying agent, 0～2 part
Stabilizer, 40～60 parts of solvent orange 2 As, 5～10 parts of solvent B.
Heavy metal ion adsorbed film the most according to claim 2, it is characterised in that described solvent orange 2 A is selected from dimethyl
One or more in Methanamide, dimethyl acetylamide, N-Methyl pyrrolidone and dimethyl sulfoxide, described solvent B
One or more in ethanol, acetone and ethyl acetate.
Heavy metal ion adsorbed film the most according to claim 3, it is characterised in that described solvent orange 2 A is dimethyl acyl
Amine, described solvent B is ethanol.
Heavy metal ion adsorbed film the most according to claim 4, it is characterised in that described modifying agent is selected from dodecane
One or more in base benzene sulfonic acid sodium salt, sodium cetanesulfonate, sodium lauryl sulphate.
Heavy metal ion adsorbed film the most according to claim 5, it is characterised in that described stabilizer is that phosphate delays
Dissolved liquid, it is formulated by disodium hydrogen phosphate and sodium dihydrogen phosphate.
Heavy metal ion adsorbed film the most according to claim 6, it is characterised in that described modifying agent is dodecyl
Sodium sulfate.
8. the preparation method of the heavy metal ion adsorbed film as described in arbitrary in claim 2～7, it is characterised in that
Including step:
The metal-organic framework material of corresponding weight portion is scattered in solvent orange 2 A by S100, adds modifying agent under stirring, heats up
To 60 DEG C, continue stirring 1～5 hour, add stabilizer and form dispersion liquid；
2-mercaptobenzimidazole is dissolved in solvent B by S200, and gained solution adds in described dispersion liquid, continues to stir at 60 DEG C
Mix 1～6 hour, obtain casting solution；
S300, by described casting solution filtering and standing deaeration 1～2 hours, is cast in glass plate, is placed in baking oven being dried；With
And
S400 is 110～120 DEG C of heat treatments 1～after 5 hours through temperature, is placed in 2mol/L sulphuric acid process 10～24 hours,
Rinse till cleaning mixture is neutrality with water afterwards, wet film is placed at 50～60 DEG C vacuum drying and has obtained 2-sulfydryl immobilized
The metal-organic framework material composite membrane of benzimidazole, prepares described heavy metal ion adsorbed film.
Preparation method the most according to claim 8, it is characterised in that metal organic frame material in described preparation method
Material and 2-mercaptobenzimidazole mass ratio are 4: 1, and solvent orange 2 A and solvent B mass ratio are 8: 1.
Preparation method the most according to claim 9, it is characterised in that the metal in described step S100 has machine frame
The synthesis of frame material includes step:
The ferric chloride hexahydrate of respective quality is dissolved in deionized water by S110, and stirring is fully dissolved, and adds equal benzene front three
Acid, continues stirring 0.5 hour；
Above-mentioned solution is loaded autoclave 130 DEG C and reacts 72 hours by S120；And
S130 is cooled to room temperature after the solution reaction of step S120 terminates, and washes three times with hot water and methanol, and at boiling methanol
Middle process 12 hours, 150 DEG C are vacuum dried 12 hours, obtain metal-organic framework material.
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| CN114011384A (en) * | 2021-11-03 | 2022-02-08 | 浙江大学 | Film for removing heavy metal ions in water and performing fluorescence detection and preparation method thereof |
| CN114486824A (en) * | 2021-12-27 | 2022-05-13 | 南京大学 | Soil system-oriented high-resolution technology-coupled heavy metal in-situ characterization system for simulating pH change |
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