CN114225921B - Preparation method of mercury ion imprinting adsorption material - Google Patents
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 60
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960001748 allylthiourea Drugs 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 21
- -1 ethylene glycol dimethyl acrylic acid methyl ester Chemical compound 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 2
- YVUZUKYBUMROPQ-UHFFFAOYSA-N mercury zinc Chemical group [Zn].[Hg] YVUZUKYBUMROPQ-UHFFFAOYSA-N 0.000 claims description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 11
- 229960002523 mercuric chloride Drugs 0.000 abstract description 6
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 abstract description 6
- 239000003463 adsorbent Substances 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003546 flue gas Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 12
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000009388 chemical precipitation Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 125000002133 (4-hydroxy-3-iodo-5-nitrophenyl)acetyl group Chemical group OC1=C(C=C(C=C1I)CC(=O)*)[N+](=O)[O-] 0.000 description 1
- AOIDYWIUVADOPM-UHFFFAOYSA-N 2-hydroxyethyl 2,3-dimethylbut-2-enoate Chemical compound CC(C)=C(C)C(=O)OCCO AOIDYWIUVADOPM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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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
- B01J20/28016—Particle form
-
- 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
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/202—Polymeric adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a mercury ion imprinting adsorption material, which comprises the steps of mixing a mercuric chloride solution and allylthiourea according to a mol ratio of 1:2-4, adding a methanol solution, adding a functional monomer into the mixed solution according to a mol ratio of 2:1-6, and stirring for 1h at room temperature to form a mercury ion complex; the functional monomer is N, N-dimethylformamide; oscillating the mercury ion complex for 2 hours, and then mixing the mercury ion complex with the catalyst according to a mol ratio of 20-60:1, adding ethylene glycol dimethyl methyl acrylate and azodiisobutyronitrile, introducing inert gas for 10min, and oscillating in a water bath kettle at 60 ℃ for 24h to form polymer solid; and crushing and sieving the polymer solid to polymer particles of 30-38.5 mu m, and vacuum drying at 35 ℃ to obtain the mercury ion imprinted polymer. The polymer ion imprinting material has good adsorption capacity on divalent mercury in water and gas phase, and is an effective adsorbent for Hg (II) in high-efficiency flue gas.
Description
Technical Field
The invention belongs to the technical field of mercury ion imprinting adsorption, and particularly relates to a preparation method of a mercury ion imprinting adsorption material.
Background
The method is a global maximum mercury production, use and discharge country, and in the aspect of water pollution, heavy metal mercury pollution is generally difficult to treat, and mercury-containing wastewater treatment can only be mercury ion phase transfer or change the physical and chemical states of mercury ions because mercury ions cannot be decomposed and destroyed. The treatment method of mercury metal waste water mainly comprises chemical precipitation method, ion exchange method, evaporation concentration method, electrolytic method, liquid film method, adsorption method, etc. At present, the mercury-containing wastewater is treated by a chemical precipitation method in industry. The application technology of the chemical precipitation method is easy to realize, and particularly, the method has good performance and excellent cost performance in the treatment of wastewater with high heavy metal content. However, the chemical precipitation method has the defects of easy water hardening, incomplete treatment of low-concentration mercury wastewater due to the influence of solubility product, easy secondary pollution, difficult application to treatment of flowing water bodies and the like. Therefore, a method for preparing the mercury ion imprinting adsorbing material is needed.
Disclosure of Invention
The invention provides a preparation method of a mercury ion imprinting adsorption material.
The invention comprises the following steps:
mixing a mercuric chloride solution and allylthiourea according to a mol ratio of 1:2, adding a methanol solution, and stirring for 1h at room temperature to obtain a mixed solution;
adding a functional monomer into the mixed solution according to a mol ratio of 2:1-6, and stirring for 1h at room temperature to form a mercury ion complex; the functional monomer is N, N-dimethylformamide;
c, oscillating the mercury ion complex for 2 hours, and then according to the mol ratio of 40:1, adding ethylene glycol dimethyl acrylic acid methyl ester and azodiisobutyronitrile, introducing inert gas for 10min, and oscillating in a water bath kettle at 60 ℃ for 24h to form polymer solid, wherein the inert gas is nitrogen;
and D, crushing and sieving the polymer solid to polymer particles of 30-38.5 mu m, repeatedly washing the polymer solid with 0.5% thiourea and HNO3 solution until mercury ions are not detected in the eluent, and drying the polymer solid in vacuum at 35 ℃ overnight to obtain the mercury ion imprinted polymer (MIP).
Further, in the step A, the stirring speed was 500rpm and the stirring time was 0.5h.
Further, in step D, HNO 3 The concentration of the solution was 0.5mol/L.
The application of the mercury ion molecularly imprinted adsorption material in adsorbing mercury ions is provided.
Further, adding a proper amount of mercury ion molecular imprinting adsorbent into the wastewater containing mercury ions, adjusting the pH to 3-7, and adsorbing for 1-8h under the conditions that the temperature is 20-40 ℃ and the rotating speed of a shaking table is 80-100 rpm.
Further, the wastewater is zinc mercury wastewater.
The beneficial effects of the invention are as follows:
the polymer ion imprinting material has good adsorption capacity to divalent mercury in water and gas phase, and the adsorption capacity reaches 36579 mug/g; the mercury-related environment-friendly functional material has excellent Hg (II) adsorption capacity and regeneration capacity, and is an effective adsorbent for Hg (II) in high-efficiency flue gas.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a mercury ion imprinted polymer;
FIG. 2 is a schematic diagram of a mercury ion imprinted polymer equilibrium adsorption experiment;
FIG. 3 is a schematic diagram of a mercury ion imprinted polymer adsorption kinetics experiment;
FIG. 4 is a schematic diagram of a mercury ion imprinted polymer adsorption thermodynamic experiment;
FIG. 5 is a schematic diagram of a molecular imprinting solid phase extraction process;
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
The present embodiment includes the following steps:
example 1
To a solution of 2mmol of mercuric chloride, 4mmol of allylthiourea was added in a molar ratio of 1:2, dissolved in 10mL of methanol, 10mL of LN, N-dimethylformamide was added, after shaking for 2 hours 40mmol of ethylene glycol dimethyl methacrylate, 1.12mmol of azobisisobutyronitrile initiator was added and shaking was carried out for 2 hours.
After the solution is introduced with nitrogen for 10min under the ice bath condition, the solution is oscillated for 24h in a water bath kettle at 60 ℃.
The resulting polymer was crushed and sieved to polymer particles of 30-38.5. Mu.m.
Followed by 0.5% thiourea+0.5 mol/L HNO 3 Washing to no Hg 2 + detection. Vacuum drying overnight at 35 ℃ to obtain mercury ion imprinted polymer (MIP).
The synthetic procedure for NIP is completely identical to that for synthetic MIP, except that no template molecule is added during synthesis. The obtained polymers were subjected to adsorption experiments and characterization, respectively. The specific synthesis and characterization steps are shown in figure 1 below.
Adsorption experiments on polymers
(1) Equilibrium adsorption experiments
10.0mg of MIP or NIP powder is placed in a 10mL sample bottle, 8mL of mercuric chloride solution with different concentrations is added, the mixture is oscillated for 24h at room temperature, the solution is centrifuged for 3min at 6000rpm, and the supernatant is detected by atomic absorption. The concentration of the solution after adsorption was obtained from the standard curve, and the adsorption capacity was calculated from the change in the concentration of the solution before and after adsorption.
The equilibrium adsorption experiments were performed in ultra pure water solution, not in methanol solution, mainly considering that the actual sample to be detected later is tap water or river water. As can be seen from FIG. 2, within the experimental concentration range, the MIP adsorbs Hg 2 The + capacity is superior to NIP. The difference in these experimental data between MIPs and NIPs further illustrates the presence of specific recognition sites for MIPs.
(2) Adsorption kinetics experiments
10.0mg of MIP and NIP powder are placed in 10mL sample bottles respectively, 8mL 1500ppm mercuric chloride solution is added, the mixture is oscillated at room temperature, solutions are taken at different times (5 min,10min,20min,30min, 1h,2h,4h,8h,10h,24 h) respectively, the solutions are centrifuged at 6000rpm for 3min, and the clear solution is detected by atomic absorption. As shown in fig. 3, the concentration of the solution after adsorption was obtained from a standard curve, the adsorption capacity was calculated from the change in the concentration of the solution before and after adsorption, and an adsorption kinetics curve was drawn.
To measure polymer versus Hg 2 Adsorption rate of+ MIP and NIP dynamic adsorption experiments were performed, respectively. As shown in fig. 2-5, the MIP adsorbed quickly during the first 2 hours, and then gradually slowed down, and reached substantially saturated adsorption after 4 hours. This is mainly because Hg is present in the initial stage 2 +is easily adsorbed by the holes of the polymer surface layer, hg once the holes of the surface layer are occupied 2 The + needs to be transported into the interior of the polymer to be adsorbed by the internal holes, which takes more time. The same experiment was also performed on NIP, and the result shows that the NIP adsorption speed is fast in the first 1h, then the speed is fast and slow down, and the saturated adsorption is basically reached after 2h. And the adsorption amount of NIP is smaller than that of MIP. The difference between the two may be due to the specific adsorption of MIPs.
(3) Adsorption thermodynamic experiments
10.0mg of MIP and NIP powder were placed in 10mL sample bottles, 8mL 1500ppm mercuric chloride solution was added, the solutions were taken at 20℃and 40℃and 60℃respectively, centrifuged at 6000rpm for 3min at different times, and the supernatant was examined by atomic absorption. As shown in fig. 4, the concentration of the solution after adsorption was obtained from a standard curve, the adsorption capacity was calculated from the change in the concentration of the solution before and after adsorption, and an adsorption kinetics curve was drawn.
Adsorption isotherm
Langmuir and Freundlich isotherms are two modes that are commonly used to describe adsorption experiments.
Langmuir adsorption isothermic type is mainly applied to single-layer adsorption of smooth homogeneous surfaces, and Freundlich adsorption isothermic type is widely applied to adsorbents with non-uniform distribution of surface energy.
Langmuir adsorption isothermic formula is:
q in max And K L For Langmuir adsorption characteristic parameters, C can be drawn e Pair C of qe e The slope and intercept of the curve are obtained.
Freundlich adsorption isothermic formula:
q＝k f Ce 1/n (2)
this formula may also be the following linear relationship:
ln(q e )＝ln(k f )+(1/n ln(C e )) (3)
where Kf and n are adsorption capacity factors and adsorption indexes, and are obtained by plotting ln (qe) against ln (Ce).
TABLE 3-1 Mercury ion imprinted Polymer adsorption thermodynamic analysis
(3) Material adsorption evaluation results
Polymer solid phase extraction process and preparation of sample (Hg in water body 2+ )
The polymer solid phase extraction column (MISPE) is obtained by ultrasonic cleaning the solid phase extraction column with chromatographic pure methanol for 30min and then loading 200mg of polymer. The MIPE column was then activated with 10mL of methanol and 10mL of ultrapure water. The water sample flows through the MISPE column at the speed of 2-3 mL/min, and then 0.5 percent thiourea and 0.5mol/L HNO of 90:10 (v/v) are used 3 The eluate was detected with RA 915.
And (3) carrying out enrichment and separation processes on the water sample in the polymer solid phase extraction column. The freshly taken water sample was passed through a 0.45 μm membrane to remove suspended matter from the water and acidified to pH 2.0 with phosphoric acid. The specific molecular imprinting solid phase extraction process is shown in fig. 5.
The polymer ion imprinting material has good adsorption capacity to divalent mercury in water and gas phase, and the adsorption capacity reaches 36579 mug/g; the mercury-related environment-friendly functional material has excellent Hg (II) adsorption capacity and regeneration capacity, and is an effective adsorbent for Hg (II) in high-efficiency flue gas.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art who is skilled in the art to which the present invention pertains will appreciate that they can be substituted or altered according to the technical scheme and the inventive concept thereof within the scope of the present invention.
Claims (4)
1. The preparation method of the mercury ion imprinting adsorption material is characterized by comprising the following steps of:
a, mercury chloride solution and allylthiourea are mixed according to a molar ratio of 1:2-4, adding a methanol solution after mixing, and stirring for 1h at room temperature to obtain a mixed solution;
b in the mixed solution according to a mole ratio of 2:1-6 adding functional monomers, and stirring for 1h at room temperature to form mercury ion complexes; the functional monomer is N, N-dimethylformamide;
c, oscillating the mercury ion complex for 2 hours, and then mixing the mercury ion complex with the catalyst according to a molar ratio of 20-60:1 adding ethylene glycol dimethyl acrylic acid methyl ester and azodiisobutyronitrile, introducing inert gas for 10min, and oscillating in a water bath kettle at 60 ℃ for 24h to form polymer solid, wherein the inert gas is nitrogen;
d crushing and sieving the polymer solid to polymer particles of 30-38.5 mu m, and then using 0.5% thiourea and HNO 3 Washing the solution for multiple times until mercury ions are not detected in the eluent, and vacuum drying overnight at 35 ℃ to obtain mercury ion imprinted polymer;
in the step A, the stirring speed is 500rpm, and the stirring time is 0.5h;
in step D, HNO 3 The concentration of the solution was 0.5mol/L.
2. An application method of a mercury ion molecularly imprinted adsorption material in adsorbing mercury ions is characterized in that the mercury ion molecularly imprinted adsorption material is prepared by the preparation method of the mercury ion molecularly imprinted adsorption material as claimed in claim 1.
3. Application method according to claim 2, characterized in that the method is as follows: the mercury ion molecularly imprinted adsorption material prepared by the preparation method of claim 1 is added into wastewater containing mercury ions, the pH is regulated to 3-7, and the adsorption is carried out for 1-8 hours under the conditions that the temperature is 20-40 ℃ and the rotating speed of a shaking table is 80-100 rpm.
4. A method of use according to claim 3, wherein the wastewater is zinc mercury wastewater.
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