CN116371378A - Magnetic adsorption material and preparation method and application thereof - Google Patents
Magnetic adsorption material and preparation method and application thereof Download PDFInfo
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- CN116371378A CN116371378A CN202310376075.9A CN202310376075A CN116371378A CN 116371378 A CN116371378 A CN 116371378A CN 202310376075 A CN202310376075 A CN 202310376075A CN 116371378 A CN116371378 A CN 116371378A
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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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/28009—Magnetic properties
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a magnetic adsorption material, a preparation method and application thereof. The magnetic adsorption material comprises a crosslinking component, and consists of itaconic acid, acrylamide and N-allylthiourea; the functional component consists of a cross-linking agent and an initiator; and a magnetic component consisting of magnetic Fe 3 O 4 Particle composition; the crosslinking component is crosslinked and embedded into the magnetic component under the action of the functional component; wherein the mole ratio of itaconic acid to acrylamide to N-allylthiourea is 1-5:1:1; the molar ratio of the crosslinking component, the crosslinking agent and the initiator is 3-7:0.3-2:0.002-0.02; the saidThe molar ratio of the crosslinking component to the magnetic component is 3-7:0.3-1.5. The magnetic adsorption material contains multiple functional groups such as carboxyl, amino, thiourea and the like, and can simultaneously carry out Cd reaction 2+ 、Pb 2+ 、As 3+ 、Hg 2+ In addition, the magnetic adsorption material can realize high-efficiency elution under a specific eluent, and the elution rate is more than 90%, so that the magnetic adsorption material has wide application prospect in the field of heavy metal enrichment and purification.
Description
Technical Field
The invention belongs to the field of adsorption materials, and particularly relates to a magnetic adsorption material, and a preparation method and application thereof.
Background
Along with the rapid development of industry and agriculture, heavy metal pollution is one of the great problems of environmental pollution in China, and has great harm to human health and ecosystems. Heavy metals are nondegradable and easily accumulated in the human body, and are pollutants with carcinogenicity. In the field of trace heavy metal analysis and detection, efficient enrichment and purification of a sample are effective means for enabling the sample to be detected by various terminals and improving the detection sensitivity of the sample, so that the technology for enriching and purifying the heavy metal and the new material are designed and developed as hot spots and difficulties in research in the field of heavy metal analysis and detection. The common enrichment and purification methods for heavy metals include a microbial degradation method, a flocculation sedimentation method, an electrochemical method, an adsorption method and the like, wherein the adsorption method has the characteristics of high treatment speed, low pollutant residual concentration, simplicity in operation and the like.
The magnetic adsorption material has strong adsorption capacity and simultaneously has the characteristic of rapid separation from a solid phase or a liquid phase. For example: the application of biochar magnetic adsorption material in removing heavy metal cadmium is disclosed in Sho jin guang et al (publication No. CN 111085170B), wherein the primary finished product is required to be pyrolyzed at 500-600 ℃ for 1-1.5h in the preparation process, the preparation is complicated, and only the heavy metal cadmium is researched. Jiang Caiyun et al (publication No. CN 102716721B) disclose a method of using Fe 3 O 4 Novel method for treating lead-containing wastewater by using Ag magnetic core-shell nano materialThe magnetic nano material is used as a matrix, gallic acid is used as a functional group to modify the magnetic nano material, and the purpose of efficiently removing lead ions in wastewater can be achieved by using the magnetic nano material, but the magnetic nano material has no obvious effect of removing other heavy metal ions. Huo Zhibao (publication No. CN 106334527A) discloses a preparation method of a polyethylene polyamine modified biomass-based magnetic heavy metal adsorbent, which comprises the steps of reacting for 4-16 hours at 160-190 ℃ under severe synthesis conditions, wherein the adsorbent has adsorption performance on lead, cadmium and copper ions. The preparation method of the magnetic adsorption materials has harsh general synthesis conditions or can only adsorb single heavy metal ions. In addition, many magnetically attractable materials are expensive in terms of raw materials, resulting in generally high manufacturing costs.
Therefore, a novel adsorption material which has mild reaction conditions and low raw material cost and can efficiently adsorb one or more heavy metal ions is developed, and the novel adsorption material has important theoretical significance and application value.
Disclosure of Invention
In view of the foregoing problems of the prior art, a first object of the present invention is to provide a magnetically absorptive material.
A second object of the present invention is to provide a method for preparing a magnetically attractable material as described above.
A third object of the present invention is to provide a heavy metal enrichment kit comprising a magnetic adsorption material as described above.
The fourth object of the invention is to provide a pretreatment method for detecting heavy metal content in grains.
The fifth object of the invention is to provide a method for enriching and purifying heavy metals.
In order to achieve the first object, the present invention adopts the technical scheme that:
the invention discloses a magnetic adsorption material, which comprises
The crosslinking component consists of itaconic acid, acrylamide and N-allylthiourea;
the functional component consists of a cross-linking agent and an initiator;
and a magnetic component consisting of magnetic Fe 3 O 4 Particle composition;
the crosslinking component is crosslinked and embedded into the magnetic component under the action of the functional component;
wherein the mole ratio of itaconic acid to acrylamide to N-allylthiourea is 1-5:1:1;
the molar ratio of the crosslinking component, the crosslinking agent and the initiator is 3-7:0.3-2:0.002-0.02;
the molar ratio of the crosslinking component to the magnetic component is 3-7:0.3-1.5.
Aiming at the problems of complicated preparation steps, harsh conditions, single heavy metal adsorption type and the like of the magnetic adsorption material in the prior art, the invention provides a novel magnetic adsorption material and a method for preparing the magnetic adsorption material, wherein the magnetic adsorption material is prepared by inducing three polymerizable monomers to crosslink and embed magnetic Fe 3 O 4 The preparation method is simple in operation, low in raw material cost and mild in synthesis condition, is beneficial to industrial production, and the magnetic adsorption material prepared by the method contains multiple functional groups such as carboxyl, amino, thiourea and the like, can adsorb multiple heavy metal elements of limited attention such as cadmium, lead, arsenic, mercury and the like, and in addition, the aim of efficiently adsorbing heavy metal ions is fulfilled by adjusting the raw material formula of the magnetic adsorption material and generating a synergistic effect, and efficient elution is realized by matching with a specific eluent.
Further, the molar ratio of itaconic acid, acrylamide and N-allylthiourea may be 1:1:1, 2:1:1, 3:1:1, 4:1:1 or 5:1:1, etc., or intervals formed by any two ratios; preferably, when the mole ratio of itaconic acid to acrylamide to N-allylthiourea is 1:1:1, the prepared magnetic adsorption material has the best comprehensive adsorption effect on four elements of Cd, pb, as and Hg.
When the optimal molar ratio of itaconic acid, acrylamide and N-allylthiourea is determined, further consideration is given to the ratio of the crosslinking component to the crosslinking agent and initiator, which is exemplified, the molar ratio of the crosslinking component, the crosslinking agent, and the initiator may also be 3:0.5-2:0.002-0.02, 3:1-2:0.002-0.02, 3:0.5-1:0.002-0.02, 3:0.5-2:0.002-0.015, 3:0.5-2:0.002-0.01, 3:0.5-2:0.002-0.005, 3:0.5-2:0.005-0.02, 3:0.5-2:0.005-0.015, 3:0.5-2:0.005-0.01, 3:0.5-2:0.01-0.02, 3:0.5-2:0.01-0.015, 3:0.5-0.015, 3:1-2:0.002-0.002, 3:0.002-2:0.002, 3:0.002-2:0.01; 3:1-2:0.005-0.02, 3:1-2:0.005-0.015, 3:1-2:0.005-0.01, 3:1-2:0.01-0.02, 3:1-2:0.01-0.015, 3:1-2:0.015-0.02, 3:0.5-1:0.002-0.015, 3:0.5-1:0.002-0.01, 3:0.5-1:0.002-0.005, 3:0.5-1:0.005-0.02, 3:0.5-1:0.005-0.01, 3:0.5-1:0.01, 3:0.01-0.02, 3:0.5-1:0.01-0.015, 3:0.5-1:0.015, 3:0.02, 3:0.5-1:0.015-0.02, 3:0.02-2:0.005-0.02, 3:0.02-2:0.005-0.02, etc.. When the molar ratio of the crosslinking component to the crosslinking agent to the initiator is 3:2:0.02, the prepared magnetic adsorption material has the best comprehensive adsorption effect on the four elements of Cd, pb, as and Hg.
When determining the optimal molar ratio of itaconic acid, acrylamide and N-allylthiourea, it is further desirable to consider the ratio of the crosslinking component to the magnetic component, and the molar ratio of the crosslinking component to the magnetic component may be, for example, 3:0.3-1.5, 3:0.3-1.2, 3:0.3-1, 3:0.3-0.8, 3:0.3-0.5, 3:0.5-1.5, 3:0.5-1.2, 3:0.5-1, 3:0.5-0.8, 3:0.8-1.5, 3:0.8-1.2, 3:0.8-1, 3:1-1.5, 3:1-1.2, or 3:1.2-1.5, etc. When the molar ratio of the crosslinking component to the magnetic component is 3:1, the prepared magnetic adsorption material has the best comprehensive adsorption effect on four elements of Cd, pb, as and Hg.
Further, the molar ratio of itaconic acid, acrylamide and N-allylthiourea is 1:1:1;
the molar ratio of the crosslinking component, the crosslinking agent and the initiator is 3:2:0.02;
the molar ratio of the crosslinking component to the magnetic component is 3:1.
Further, the crosslinking agent is selected from the group consisting of N, N' -methylenebisacrylamide.
Further, the initiator includes, but is not limited to, one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, ammonium persulfate, potassium persulfate, benzoyl peroxide, and t-butyl benzoyl peroxide.
In one embodiment, the magnetic Fe in the present invention 3 O 4 The particles are prepared by the processes described in the literature. (Xu J, yang H B, fu W Y, et al preparation and magnetic properties of magnetite Nanoparticles sol-gel [ J)].Magn.Magm,2007:309-311.)
In order to achieve the second object, the present invention adopts the technical scheme that:
the invention discloses a method for preparing a magnetic adsorption material, which comprises the following steps:
and in inert atmosphere, adding the crosslinking component, the magnetic component and the crosslinking agent in proportion, then adding the solvent, stirring uniformly, adding the initiator, heating to the reaction temperature for reaction, and washing and drying after the reaction is finished to obtain the magnetic adsorption material.
In the preparation method, the crosslinking component is subjected to free radical polymerization under the action of a crosslinking agent and an initiator, and then the magnetic component is embedded to obtain the magnetic adsorption material, and the reaction equation is shown below. The magnetic component is added to provide magnetism for the material, which is beneficial to convenient taking out after enriching heavy metal ions, meanwhile, the inventor also discovers that the magnetic component and the crosslinking component can have synergistic effect, and the adsorption performance of the adsorption material to As is obviously enhanced after the compound use, which is probably due to the fact that the complex oxide component of iron in the magnetic component is easy to combine with As ions to form FeAsO 4 Attached to the adsorbent material.
Further, the reaction temperature is 60-80 ℃ and the reaction time is 6-24h.
Further, the solvent includes, but is not limited to, one or more of tetrahydrofuran, acetonitrile, dioxane, toluene, and water.
Further, the inert atmosphere includes a nitrogen atmosphere or an argon atmosphere.
In order to achieve the third object, the present invention adopts the technical scheme that:
the invention discloses a heavy metal enrichment kit, which comprises:
a magnetically attractable material as described above or a magnetically attractable material prepared by a method as described above.
Further, the heavy metal enrichment kit further comprises an eluent;
the eluent comprises one or more of nitric acid solution, cysteine hydrochloride solution, thiourea solution, EDTA disodium solution, naOH solution and EDTA alkali solution;
wherein the volume fraction of the nitric acid solution is 0.5-10% (v/v), preferably 1-5% (v/v); illustratively, the nitric acid solution may be 1%, 2%, 3%, 4%, 5%, etc. by volume.
The mass fraction of the cysteine hydrochloride solution is 0.5-5%, preferably 1-3%; illustratively, the cysteine hydrochloride solution is 1%, 2%, 3%, etc. by mass.
The mass fraction of the thiourea solution is 0.5-5%, preferably 1-3%; illustratively, the thiourea solution is 1%, 2%, 3%, etc. by mass.
The mass fraction of the EDTA disodium solution is 0.5-5%, preferably 1-3%; illustratively, the cysteine hydrochloride solution is 1%, 2%, 3%, etc. by mass.
The mass fraction of the NaOH solution is 0.01-0.5%, preferably 0.1-0.3%; illustratively, the NaOH solution is 0.1%, 0.2% or 0.3% by mass, etc.
The mass fraction of the EDTA alkaline solution is 0.5-5%, preferably 1-3%; illustratively, the EDTA base solution is 1%, 2% or 3% by mass, etc.; the pH value of the EDTA alkaline solution can be regulated to be one of 9 (pH is more than or equal to 8.5 and less than 9.5), 10 (pH is more than or equal to 9.5 and less than or equal to 10.5), 11 (pH is more than or equal to 10.5 and less than or equal to 11.5), 12 (pH is more than or equal to 11.5 and less than or equal to 12.5), 13 (pH is more than or equal to 12.5 and less than or equal to 13.5) and 14 (pH is more than or equal to 13.5), the EDTA alkaline solution with different pH values can be regulated by NaOH solution, and the pH value of the EDTA alkaline solution can be determined by means of a pH meter when the pH value of the EDTA alkaline solution is obtained.
Further, experiments show that when the eluent is selected from EDTA alkaline solution with the pH of 12 and 1wt%, the eluent has higher elution performance on Cd, pb, as, hg heavy metals enriched on the magnetic adsorption material, and the EDTA alkaline solution with the pH of 12 and 1wt% is determined to be the optimal eluent.
Further, the heavy metals include, but are not limited to, one or more of Cd, pb, as, and Hg.
In order to achieve the fourth object, the present invention adopts the technical scheme that:
the invention discloses a pretreatment method for detecting heavy metal content in grains, which comprises the following steps:
dispersing heavy metal-containing grains in a dilute acid solution or a cysteine hydrochloride solution by using the kit, and vortex to obtain a leaching solution;
adsorbing heavy metal ions in the leaching solution by using a magnetic adsorption material, and vortex to obtain the magnetic adsorption material enriched with the heavy metal ions;
and eluting and magnetically separating the magnetic adsorption material enriched with the heavy metal ions to obtain the treatment liquid enriched and purified with the heavy metal ions.
Further, the heavy metals include, but are not limited to, one or more of Cd, pb, as, and Hg.
Further, the heavy metal ions include, but are not limited to, cd 2+ 、Pb 2+ 、As 3+ And Hg of 2+ One or more of the following.
Further, the dilute acid solution includes, but is not limited to, one or more of dilute nitric acid, dilute hydrochloric acid, dilute sulfuric acid, oxalic acid, citric acid, lactic acid, malic acid, and acetic acid.
Further, the volume fraction of the dilute acid solution is 0.5 to 10% (v/v), preferably 1 to 5% (v/v); illustratively, the diluted acid solution may be 1%, 2%, 3%, 4%, 5%, or the like in volume fraction.
Furthermore, the leaching solution can be added with the magnetic adsorption material after the pH value of the leaching solution is adjusted to 5-9 by using NaOH solution, so that adverse effect of the dilute acid solution on the adsorption of the magnetic adsorption material is prevented, and damage of the strong acid solution on a detection instrument is reduced.
Further, the adsorption time is 1-30min; preferably 3-15min; the rotating speed of vortex is 0-2500rpm during adsorption; preferably 1000-2500rpm.
Further, the eluting time is 1-30min; preferably 5-10min; the rotational speed of the vortex is 1000-2500rpm during elution.
Further, the obtained treatment fluid can be used for further detection at the instrument end; among them, the detection devices include, but are not limited to, ICP-MS, atomic absorption spectroscopy, atomic fluorescence spectroscopy, or electrochemically related rapid detection devices, etc.; in one embodiment, the invention adopts ICP-MS for testing, and the used instrument is Agilent 8900, radio frequency power: 1550W, plasma gas flow: 15L/min, carrier gas flow: 0.85L/min, helium flow: 0.35L/min, atomizing chamber temperature: 2 ℃, sampling depth: 8mm.
In order to achieve the fifth object, the present invention adopts the technical scheme that:
the invention discloses a method for enriching and purifying heavy metals, which comprises the following steps:
And (3) adding the magnetic adsorption material into the solution containing the heavy metal ions for adsorption by using the kit, and taking out the magnetic adsorption material adsorbed with the heavy metal ions after the adsorption is finished to obtain purified supernatant.
Further, the heavy metal ion-containing solution includes a heavy metal ion solution containing one adsorbable element or a heavy metal ion solution containing a plurality of adsorbable elements; for example, when the heavy metal ion-containing solution is a heavy metal ion solution containing only one adsorbable element, the magnetic adsorption material is not affected by other element ions, so that the solid-liquid ratio of the magnetic adsorption material to the heavy metal ion-containing solution needs to be controlled to be 0.5-2mg/L, and a better enrichment effect can be achieved; such asIf the heavy metal ion-containing solution is a heavy metal ion solution containing a plurality of adsorbable elements, the magnetic adsorption material is affected by ions of other elements, and the magnetic adsorption material not only adsorbs heavy metal ions but also adsorbs ions of other elements (such as Al 3 + 、Ca 2+ 、Cu 2+ Etc.), in a specific embodiment, the invention prepares a multi-element interference environment containing 30 elements, and in order to ensure the enrichment effect of heavy metal ions, the solid-to-liquid ratio of the magnetic adsorption material to the solution containing heavy metal ions is preferably controlled to be 2-40mg/mL.
Further, the heavy metals include, but are not limited to, one or more of Cd, pb, as, and Hg.
Further, the heavy metal ions include, but are not limited to, cd 2+ 、Pb 2+ 、As 3+ And Hg of 2+ One or more of the following.
Further, a vortex mixing mode can be adopted during adsorption so as to improve the adsorption efficiency. The adsorption time is 1-30min; preferably for 10-15min; the rotating speed of vortex is 0-2500rpm during adsorption; preferably 1000-2500rpm.
Further, the solution containing heavy metal ions can be prepared by blending a single element standard solution or a multi-element standard solution; illustratively, when a single unit element adsorption experiment is carried out, a single unit element standard solution is added into an adsorption environment for adsorption test, wherein the concentration of the single unit element standard solution is 10-1000mg/L, and the single unit element standard solution is prepared by using a GBW08612 cadmium single unit element solution standard substance, a GBW08619 lead single unit element solution standard substance, a GBW08611 arsenic single unit element solution standard substance or a GBW08617 mercury single unit element solution standard substance; when a multi-element adsorption experiment is carried out, a multi-element standard solution (without mercury) containing 29 elements and a mercury standard solution are simultaneously added into an adsorption environment for adsorption test, wherein the multi-element standard solution is prepared by GBW (E) 082429 multi-element standard substances, the concentration of Cd, pb and As after preparation is 25-250 mug/L, the mercury standard solution is prepared by GBW08617 mercury unit element solution standard substances, and the Hg concentration after preparation is 5-50 mug/L.
The invention has the beneficial effects that:
the invention adopts the multi-monomer crosslinking embedding technology to successfully prepare the novel magnetic adsorption material, has excellent adsorption performance on heavy metal ions, and has the following advantages compared with the existing adsorption material:
1. the magnetic adsorption material prepared by the invention contains a plurality of functional groups such as carboxyl, amino, thiourea and the like, and can simultaneously carry out Cd reaction 2+ 、Pb 2+ 、As 3+ 、Hg 2+ When the magnetic adsorption material m-P6 is used as an adsorbent for multi-element adsorption experiments, the dosage of the magnetic adsorption material m-P6 is 50mg, the adsorption time is controlled within 15min, the effect that the adsorption rate of four elements reaches more than 85% can be achieved, and after the specific eluent is matched, high-efficiency elution can be achieved, and the elution rate can reach more than 90% after 5-10 min.
2. The invention also provides a method for preparing the material with high-efficiency adsorption performance, which adopts three polymerizable monomers to crosslink and embed magnetic Fe under the actions of a crosslinking agent and an initiator 3 O 4 The method for preparing the target material from the particles has the advantages of low raw material cost, simple synthesis operation, mild reaction conditions and the like.
3. The invention also provides a heavy metal enrichment kit which comprises a self-grinding magnetic adsorption material, can realize the efficient adsorption of heavy metal ions, and further comprises an eluent matched with the heavy metal enrichment kit, and the magnetic adsorption material for adsorbing the heavy metal ions can be eluted with high efficiency under the specific eluent.
4. The invention also provides a pretreatment method for detecting the heavy metal content in the grains, which is characterized in that the heavy metal enrichment kit is used in the leaching liquor of the grains containing the heavy metal ions, so that the enrichment of the heavy metal ions in the grains can be realized, the pretreatment efficiency in the process of analyzing and detecting the heavy metal in the grains is improved, the matrix interference is removed, the detection target object is enriched, and the detection sensitivity is improved.
5. The invention also provides a heavy metal enrichment and purification method, which is used for treating the wastewater and the waste liquid containing heavy metal ions by using the heavy metal enrichment kit, so as to realize the purification treatment of the wastewater and the waste liquid.
6. The magnetic adsorption material has good automation suitability and wide application prospect in the aspect of heavy metal detection analysis.
Drawings
FIG. 1 is a graph showing the adsorption performance of the polymer adsorbent prepared in example 1 of the present invention on heavy metals.
Fig. 2 shows a fourier infrared spectrum of the magnetic adsorption material prepared in example 2 of the present invention.
FIG. 3 shows an electron scanning microscope topography of the magnetically attractable material m-P6 of the present invention.
FIG. 4 shows the magnetic properties of the magnetically attractable material m-P6 according to the invention.
FIG. 5 shows the adsorption performance of the magnetic adsorption material m-P6 of the invention on heavy metals at different dosages.
FIG. 6 shows the elution performance of the magnetic material m-P6 according to the invention under the action of different eluents.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. It should be understood that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to further illustrate the technical means adopted by the present invention and the effects thereof, the method of the present invention is described in detail below by way of specific examples, but the present invention is not limited thereto. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and consumables, unless otherwise specified, are commercially available.
In order to obtain a polymeric adsorbent capable of more efficiently and simultaneously adsorbing a plurality of heavy metals, the applicant has carried out screening among monomers having different types of functional groups, as shown in the following table 1, first, the applicant has carried out radical polymerization of monomers having different carboxyl groups and amino groups under the action of different crosslinking agents, and has carried out 5 attempts, and these combinations have a certain adsorption effect on Cd, pb, hg (see table 2), but have no adsorption effect on As.
TABLE 1 different types of vinyl monomers and crosslinking agents
Weighing two monomers Ita and Aa, respectively 5mmol, adding 10mmol of cross-linking agent MBA into a two-neck flask, filling argon, adding 50-100mL of ultra-dry THF solvent to stir and dissolve the monomers, dissolving initiator AIBN (0.1 mmol) into 2mL of THF, injecting into a reaction bottle under the protection of argon, heating to 60 ℃ for reaction, reacting for 24 hours under strong stirring, stopping heating after the reaction is finished, recovering to room temperature, and respectively using deionized water and 1% HNO for the reactants 3 And (v/v) and absolute ethyl alcohol, and obtaining the polymer adsorption material which is marked as P1 after vacuum drying.
Because the main object of scientific research of the unit of the invention is grain and oil food, the selected standard substance and the prepared concentration are also used for meeting the industry requirements of grain and oil food detection. In order to better restore the real grain and oil food detection, the adsorption capacity of the polymer adsorption material P1 to Cd, pb, as, hg heavy metal ions is examined under the environment of multi-element interference, and the steps are as follows:
preparing a heavy metal standard solution: preparing a multi-element standard solution with the concentration of 250 mug/L by using a multi-element mixed standard substance GBW (E) 082429 containing 29 ions; the standard substance of the GBW08617 mercury unit element solution is prepared into the Hg standard solution with the concentration of 50 mug/L.
Multielement adsorption experiment: weighing polymer adsorption material P1 mg, placing in a centrifuge tube, adding 4mL of pure water, and taking 0.5mL of multi-element standard solution with concentration of 250 mug/L and 0.5mL of Hg standard solution with concentration of 50 mug/L as multi-element interference environmentVortex the centrifuge tube for 15min to make it fully adsorb, centrifugate (8000 rpm) and then take 0.5mL of clear liquid, add 4.5mL of 5% HNO 3 (v/v) dilution of the solution, residual concentration of Cd, pb, as, hg and adsorption rate of P1 were measured by ICP-MS for the diluted sample, as shown in Table 2.
Attempt 2
The crosslinking agent in trial 1 was changed to EDMA,10mmol, and the other experimental conditions were the same as those in trial 1. The obtained polymer adsorbent was designated as P2, and adsorption performance was examined with reference to the multi-element adsorption experiment in attempt 1, and the obtained results are shown in table 2.
Attempt 3
The monomer combination in trial 1 was changed to Ita and V-Ia, 5mmol each, and the other experimental conditions were the same as those in trial 1. The obtained polymer adsorbent was designated as P3, and adsorption performance was examined with reference to the multi-element adsorption test in attempt 1, and the obtained results are shown in table 2.
Attempt 4
The monomer combination in trial 1 was changed to Ma and Aa, 5mmol each. Other experimental conditions were the same as in trial 1. The obtained polymer adsorbent was designated as P4, and adsorption performance was examined with reference to the multi-element adsorption test in attempt 1, and the obtained results are shown in table 2.
Attempt 5
The monomer combination in trial 1 was changed to MAs and Aa, 5mmol each. Other experimental conditions were the same as in trial 1. The obtained polymer adsorbent was designated as P5, and adsorption performance was examined with reference to the multi-element adsorption test in attempt 1, and the obtained results are shown in table 2.
Table 2 summary of adsorption experimental data
In order to increase the adsorption of As by the polymer adsorption material, two monomers containing S are respectively introduced into the raw materials based on the formula of the P1 raw materials, and an attempt 6 and an attempt 7 are carried out.
Attempt 6
The monomer combination in trial 1 was changed to Ita, aa, ATU, 5mmol each, and the other experimental conditions were the same as those in trial 1. The obtained polymer adsorbent was designated as P6, and adsorption performance was examined with reference to the multi-element adsorption test in attempt 1, and the obtained results are shown in table 3.
Attempt 7
The monomer combinations in trial 1 were changed to Ita, aa, S-all-L-cys, 5mmol each, and the other experimental conditions were the same as in trial 1. The obtained polymer adsorbent was designated as P7, and adsorption performance was examined with reference to the multi-element adsorption test in attempt 1, and the obtained results are shown in table 3. P6 and P7 had a certain adsorption performance on Cd, pb, as, hg, and the effect of P6 was significantly better than that of other experimental groups, so that further studies were conducted with the raw material formulation of P6.
Table 3 summary of adsorption experimental data
Example 1
In this embodiment, based on the raw material formulation of P6, a single-factor experiment was designed to determine the optimum ratio of each monomer to the crosslinking agent, and the specific preparation steps are as follows:
weighing three monomers Ita, aa, ATU and a crosslinking agent MBA, adding the three monomers and the crosslinking agent MBA into a two-neck flask with the proportion of 5mmol being 1 equivalent as shown in table 4, filling argon, adding 50-100mL of ultra-dry THF solvent to stir and dissolve the monomers, dissolving an initiator AIBN (0.1 mmol) into 2mL of THF, injecting into a reaction bottle under the protection of the argon, heating to 60 ℃ for reaction, reacting for 24 hours under strong stirring, stopping heating after the reaction is finished, recovering to room temperature, and respectively using deionized water and 1% HNO for the reactants 3 And (v/v) and absolute ethyl alcohol, and obtaining the polymer adsorption materials which are respectively marked as P6 and P8-P13 after vacuum drying.
Table 4 Single factor designs the ratios of the monomers in the experimental conditions
| Material serial number | Ita(equiv.) | Aa(equiv.) | ATU(equiv.) | MBA(equiv.) |
| |
1 | 1 | 1 | 0.5 |
| |
1 | 1 | 1 | 1 |
| |
1 | 1 | 1 | 2 |
| |
1 | 1 | 1 | 4 |
| |
1 | 1 | 0.5 | 2 |
| |
1 | 0.5 | 1 | 2 |
| P13 | 0.5 | 1 | 1 | 2 |
The polymer adsorption materials P6 and P8-P13 carry out limit adsorption test on Cd, pb, as, hg four heavy metal ions under the environment of multi-element interference, and the steps are as follows:
preparing a heavy metal standard solution: preparing a multi-element standard solution with the concentration of 250 mug/L by using a multi-element mixed standard substance GBW (E) 082429 containing 29 ions; the standard substance of the GBW08617 mercury unit element solution is prepared into the Hg standard solution with the concentration of 50 mug/L.
Multielement adsorption experiment: respectively weighing 100mg of polymer adsorption materials P6 and P8-P13, placing into a centrifuge tube, respectively adding 4mL of pure water, 0.5mL of multi-element standard solution with the concentration of 250 mug/L and 0.5mL of Hg standard solution with the concentration of 50 mug/L as multi-element interference environments, swirling the centrifuge tube for 15min to enable the centrifuge tube to fully adsorb, centrifuging (8000 rpm), taking 0.5mL of clear liquid, and adding 4.5mL of 5% HNO 3 (v/v) dilution of the solution, and the residual concentration of Cd, pb, as, hg and the adsorption rates of P6 and P8-P13 were measured by ICP-MS for the diluted sample (FIG. 1 and Table 5).
As shown in fig. 1 and table 5, the polymer adsorption materials P6 and P8-P13 all have a certain adsorption effect on Cd, pb, as, hg four heavy metals, but when the dosage of ATU is reduced, the adsorption effect of P11 on As is obviously reduced to below 10%; when the amount of Ita containing carboxyl group or Aa containing amino group is reduced, the adsorption properties of Cd and Pb are remarkably lowered; moreover, in P6, P8-P10, the molar ratio Ita: aa: ATU: MBA=1:1:1:0.5-1:1:1:4, the decrease or increase in the amount of the crosslinking agent leads to a decrease in the adsorption performance, and particularly has a greater influence on As and Hg, and when the molar ratio Ita: aa: ATU: MBA is 1:1:2, the adsorption ratio of the obtained polymer adsorbent P6 to Cd, pb, as and Hg is 99.7%, 98.9%, 47.2% and 85.8%, respectively, and the monomer ratio of the adsorbent P6 in this group of examples is the optimum ratio, which is the monomer ratio in the preparation of a magnetic material in the following example 2 As an important reference.
Table 5 summary of adsorption experimental data
Comparative example 1
The initiator AIBN in example 1 was changed to APS, the solvent THF was changed to pure water, the reaction temperature was changed to 80℃and the other experimental conditions were the same as in example 1, and the monomer combination and the amount of the crosslinking agent were referred to as P6. The obtained polymer adsorption material is marked as P14, the water solubility is enhanced, and the yield is obviously reduced. Meanwhile, the adsorption performance is examined by referring to the multi-element adsorption experiment in the embodiment 1, and the result shows that the adsorption rate is as follows: cd:88.9%; pb:93.9%; as:35.9%; hg:78.3%.
Example 2
In order to ensure that the high molecular adsorption material has stronger adsorption capacity and is convenient for being effectively separated from a solid phase or a liquid phase to realize elution and other testing operations, the applicant embeds magnetic Fe by crosslinking 3 O 4 The method of the particles prepares the magnetic adsorption material. The ratio of the monomer to the crosslinking agent in the method is as follows with reference to the formulation of the polymer adsorbent material P6 in example 1:
three monomers Ita, aa, ATU, 5mmol each, crosslinker MBA,10mmol, magnetic Fe were weighed out 3 O 4 Adding 5mmol of particles into a two-neck flask together, filling argon, adding 50mL of ultra-dry THF solvent to stir and dissolve monomers, dissolving an initiator AIBN (0.1 mmol) into 2mL of THF, injecting into a reaction bottle under the protection of argon, heating to 60 ℃ for reaction, reacting for 24 hours under strong stirring, stopping heating after the reaction is finished, recovering to room temperature, and respectively using deionized water and 1% HNO for the reactants 3 And (v/v) washing with absolute ethyl alcohol, and finally adsorbing and removing a non-magnetic part by using a strong magnet, and obtaining a magnetic adsorbing material which is marked as m-P6 after vacuum drying.
FIG. 2 is a Fourier infrared transformation spectrum of the present embodiment, respectively magnetic Fe 3 O 4 Particle, polymer adsorption material P6 and substance structure of magnetic adsorption material m-P6 and related coordination functional groups, magnetic Fe 3 O 4 The particle and the magnetic adsorption material m-P6 are both 550-600cm -1 The telescopic vibration absorption peak of Fe-O appears near the spectral band, which indicates magnetic Fe 3 O 4 The particles were successfully embedded in the magnetically attractable material m-P6. The characteristic peaks of the polymer adsorption material P6 and the magnetic adsorption material m-P6 are similar and are 3450cm -1 A wider characteristic peak appears near the spectral band, which belongs to the N-H stretching vibration characteristic peak of O-H and amino in carboxylic acid, 1720-1706cm -1 The characteristic peak of C=Ocarbonyl is visible in the polymer adsorbent material P6, while in the magnetic adsorbent material m-P6, fe is due to magnetism 3 O 4 The addition of the particles resulted in a certain change in the vibration amplitude of the carbonyl group, so that the characteristic peak had a red shift, which also indicated that during the synthesis, magnetic Fe 3 O 4 The particles are well embedded. P6 and m-P6 are 1650-1200cm -1 The absorption peak of (C) is similar, and the variable angle vibration of N-H is 1650-1500cm -1 Near the spectral band, the telescoping vibration of thiourea N-C=S is 1500-1350cm -1 Nearby.
FIG. 3 is a Scanning Electron Microscope (SEM) topography of the present embodiment, wherein A in FIG. 3 is a morphology enlarged to 5 μm, the magnetic adsorption material m-P6 presents irregular particles, the surface is rough and uneven, and after the amplification to 500nm, a large number of hole sites on the surface of the magnetic adsorption material m-P6 can be clearly seen to promote adsorption performance.
FIG. 4 is a graph showing the hysteresis of magnetic property analysis in this example, wherein the coercivity H of the magnetic particles is equal to 0 when the applied magnetic field H is c And the remanent magnetization M r All are 0, indicating that the prepared m-P6 has superparamagnetism. And m-P6 shows magnetic properties with Fe 3 O 4 The similar magnetization of the particles indicates that the magnetic response of the magnetic material is not greatly affected by the monomers, cross-linking agents and other substances used in the synthesis during the preparation of m-P6.
Single element adsorption experiment: preparing a GBW08612 cadmium unit element solution standard substance, a GBW08619 lead unit element solution standard substance, a GBW08611 arsenic unit element solution standard substance and a GBW08617 mercury unit element solution standard substance into aqueous solutions with the concentration of 10-100mg/L respectively, then adding a magnetic adsorption material m-P6 into the aqueous solutions containing heavy metal ions respectively to form an adsorption system, wherein the solid-to-liquid ratio is 0.5mg/L, carrying out ICP-MS detection after the adsorption for 15min under vortex at 25 ℃ and 2500rpm, and determining that the saturated adsorption capacity of the magnetic adsorption material m-P6 to Cd is 215mg/g, the saturated adsorption capacity of the magnetic adsorption material m-P6 to Pb is 272mg/g, the saturated adsorption capacity of the magnetic adsorption material m-P6 to As is 287mg/g and the saturated adsorption capacity of the magnetic adsorption material m-P6 to Hg is 90mg/g.
Example 3
The magnetic adsorption material m-P6 in the embodiment 2 is subjected to limited adsorption test on Cd, pb, as, hg four heavy metal ions in a multi-interference environment, and the optimal dosage is selected.
Preparing a heavy metal standard solution: preparing a multi-element standard solution with the concentration of 250 mug/L by using a multi-element mixed standard substance GBW (E) 082429 containing 29 ions; the standard substance of the GBW08617 mercury unit element solution is prepared into the Hg standard solution with the concentration of 50 mug/L.
Multielement adsorption experiment: respectively weighing magnetic adsorption materials m-P6 with the amounts of 10mg, 20mg, 50mg and 100mg, placing into a centrifuge tube, respectively adding 4mL of pure water, 0.5mL of multi-element standard solution with the concentration of 250 mug/L and 0.5mL of Hg standard solution with the concentration of 50 mug/L as multi-element interference environments, swirling the centrifuge tube for 15min to enable the centrifuge tube to fully adsorb, fixing m-P6 with a strong magnet, and taking0.5mL of clear solution was added with 4.5mL of 5% HNO 3 (v/v) dilution of the solution, and the remaining concentration of Cd, pb, as, hg and the adsorption rate of m-P6 were measured by ICP-MS for the diluted sample.
FIG. 5 and Table 6 are graphs showing the adsorption performance of different amounts of m-P6 on Cd, pb, as, hg four heavy metal ions in a multi-element interference environment, and it can be seen that the multi-element interference on As is small, and the adsorption rate of 10mg of m-P6 on As ions reaches 90%; the adsorption effect of the four heavy metal ions is over 85%, the dosage of m-P6 is at least 50mg, namely, the adsorption rates of Cd, pb, as, hg heavy metal ions are 92.4%, 86.1%, 95.4% and 94.8% respectively; when the m-P6 dosage is 100mg, the adsorption rate of the four elements reaches more than 90 percent. And finally determining that the minimum dosage of the magnetic adsorption material with the same amount of heavy metals in the multi-element interference environment is 50mg, and adopting the magnetic adsorption material with the dosage of 50mg in the following examples and comparative examples.
Adding magnetic Fe 3 O 4 The adsorption performance of m-P6 on As after the particles is obviously enhanced, presumably because the complex oxide component of iron in the magnetic beads is easy to combine with As ions to form FeAsO 4 Attached to the adsorbent material. However, at the same time, as chelating coordination is formed between functional groups (such as carboxyl and amino) in the magnetic adsorption material and Fe, a part of functional groups favorable for adsorbing Cd and Pb are consumed, and the adsorption rate of the magnetic adsorption material on Cd and Pb is reduced.
Table 6 summary of adsorption experimental data
Comparative example 2
The molar ratio between the monomers in example 2 was changed to Ita:aa:ATU=5:1:1, 25mmol, 5mmol, respectively, and the other experimental conditions were the same as in example 2. The obtained magnetic adsorption material is marked as m-Pr1, the single element adsorption experimental process and conditions thereof are referred to example 2, and the saturated adsorption quantity result is as follows: cd:265mg/g; pb:304mg/g; as:161mg/g; hg:64mg/g. According to the conditions of example 3, the multi-element adsorption experiment is carried out on Cd, pb, as, hg four heavy metal ions in a multi-element interference environment, and the obtained adsorption rate is as follows: cd:99.8%; pb:92.1%; as:61.4%; hg:63.0%.
Comparative example 3
The molar ratio between the monomers in example 2 was changed to Ita:aa:ATU=2:1:1, 10mmol, 5mmol, respectively, and the other experimental conditions were the same as in example 2. The obtained magnetic adsorption material is marked as m-Pr2, the single element adsorption experimental process and conditions thereof are referred to example 2, and the saturated adsorption quantity result is as follows: cd:220mg/g; pb:282mg/g; as:247mg/g; hg:78mg/g. The multi-element adsorption experiment is carried out on Cd, pb, as, hg four heavy metal ions under the multi-element interference environment according to the condition test of the embodiment 3, and the obtained adsorption rate is: cd:98.7%; pb:89.6%; as:88.0%; hg:85.8%.
Comparative example 4
The molar ratio of monomer to crosslinker in example 2 was changed to Ita:aa:ATU:MBA=1:1:1:1, and 5mmol of each of the three monomers and crosslinker was used, with the other experimental conditions being the same as in example 2. The obtained magnetic adsorption material is marked as m-Pr3, the single element adsorption experimental process and conditions thereof are referred to example 2, and the saturated adsorption quantity result is as follows: cd:222mg/g; pb:270mg/g; as:157mg/g; hg:63mg/g. The multi-element adsorption experiment is carried out on Cd, pb, as, hg four heavy metal ions under the multi-element interference environment according to the condition test of the embodiment 3, and the obtained adsorption rate is: cd:96.9%; pb:88.7%; as:53.4%; hg:55.4%.
Comparative example 5
The molar ratio of monomer to crosslinker in example 2 was changed to Ita:aa:ATU:MBA=1:1:1:0.3, 5mmol of the three monomers, 1.5mmol of crosslinker, and the other experimental conditions were the same as in example 2. The obtained magnetic adsorption material is marked as m-Pr4, the single element adsorption experimental process and conditions thereof are referred to example 2, and the saturated adsorption quantity result is as follows: cd:201mg/g; pb:252mg/g; as:179mg/g; hg:56mg/g. The multi-element adsorption experiment is carried out on Cd, pb, as, hg four heavy metal ions under the multi-element interference environment according to the condition test of the embodiment 3, and the obtained adsorption rate is: cd:96.8%; pb:85.2%; as:54.0%; hg:55.3%.
Comparative example 6
Monomer and magnetic Fe in example 2 3 O 4 The mole ratio of the particles is changed to Ita, aa, ATU and Fe 3 O 4 =1:1:1:1.5, three monomers 5mmol, fe 3 O 4 Other experimental conditions were the same as in example 2, except that 7.5mmol was used. The obtained magnetic adsorption material is marked as m-Pr5, the single element adsorption experimental process and conditions thereof are referred to example 2, and the saturated adsorption quantity result is as follows: cd:165mg/g; pb:223mg/g; as:272mg/g; hg:73mg/g. The multi-element adsorption experiment is carried out on Cd, pb, as, hg four heavy metal ions under the multi-element interference environment according to the condition test of the embodiment 3, and the obtained adsorption rate is: cd:81.3%; pb:75.6%; as:94.6%; hg:77.8%.
Comparative example 7
Monomer and magnetic Fe in example 2 3 O 4 The mole ratio of the particles is changed to Ita, aa, ATU and Fe 3 O 4 =1:1:1:0.3, three monomers 5mmol, fe 3 O 4 1.5mmol, the other experimental conditions were the same as in example 2. The obtained magnetic adsorption material is marked as m-Pr6, the single element adsorption experimental process and conditions thereof are referred to example 2, and the saturated adsorption quantity result is as follows: cd:156mg/g; pb:209mg/g; as:107mg/g; hg:76.5mg/g. The multi-element adsorption experiment is carried out on Cd, pb, as, hg four heavy metal ions under the multi-element interference environment according to the condition test of the embodiment 3, and the obtained adsorption rate is: cd:76.8%; pb:80.6%; as:69.2%; hg:70.4%.
Comparative example 8
The molar ratio of monomer to initiator AIBN in example 2 was changed to Ita: aa: ATU: AIBN=1:1:1:100, i.e. initiator AIBN was 0.05mmol, reaction time was 6h, and the other experimental conditions were the same as in example 2. The obtained magnetic adsorption material is marked as m-Pr7, the single element adsorption experimental process and conditions thereof are referred to example 2, and the saturated adsorption quantity result is as follows: cd:228mg/g; pb:257mg/g; as:285mg/g; hg:78mg/g. The multi-element adsorption experiment is carried out on Cd, pb, as, hg four heavy metal ions under the multi-element interference environment according to the condition test of the embodiment 3, and the obtained adsorption rate is: cd:96.8%; pb:88.6%; as:98.4%; hg:89.9%.
Comparative example 9
The initiator system AIBN/THF in example 2 was changed to the water-soluble initiator system APS/H 2 O, the molar ratio of monomer to initiator APS was also changed to Ita:aa:ATU:APS=1:1:1:500, i.e. initiator APS was 0.01mmol, the reaction temperature was 80℃and the other experimental conditions were the same as in example 2. The obtained magnetic adsorption material is marked as m-Pr8, the single element adsorption experimental process and conditions thereof are referred to example 2, and the saturated adsorption quantity result is as follows: cd,166mg/g; pb,181mg/g; as,63mg/g; hg,70mg/g. The multi-element adsorption experiment is carried out on Cd, pb, as, hg four heavy metal ions under the multi-element interference environment according to the condition test of the embodiment 3, and the obtained adsorption rate is: cd,86.8%; pb,65.6%; as,44.0%; hg,75.4%.
Example 4
The magnetic adsorption material m-P6 described in example 2 was subjected to elution performance tests under different eluents.
Preparing an eluent: respectively preparing 1% HNO 3 (v/v) solution, 1wt% cysteine hydrochloride (CysH) solution, 1wt% Thiourea (TU) solution, 1wt% disodium EDTA (ENa) 2 ) Solutions, 0.1wt% NaOH solutions, and 1wt% EDTA solutions formulated with NaOH at different pH values (including pH 9, 1wt% EDTA solution designated E9, pH 12, 1wt% EDTA solution designated E12, pH 14, 1wt% EDTA solution designated E14).
Adsorption conditions: heavy metal adsorption was performed according to the multi-element adsorption test of example 3, the amount of the magnetic adsorption material m-P6 was 50mg, and after confirming adsorption of four heavy metals, m-P6 was fixed with a strong magnet, the supernatant was poured out, and washed with pure water 2 times for use.
Elution experiment: respectively placing m-P6 with heavy metal adsorbed into 5mL of the above different eluents, swirling for 15min, fixing m-P6 with strong magnet to obtain supernatant 0.5mL, adding 4.5mL of 5% HNO 3 (v/v) dilution of the solution, and the diluted sample was measured for the concentration and elution rate of Cd, pb, as, hg by ICP-MS.
FIG. 6 and Table 7 show the elution effect of the eluent on m-P6, as can be seen at 1% HNO 3 Under the action of the acidic eluent, only Pb can be eluted well, and all the other three elements cannot be eluted. Some of the Cd, pb, hg can be eluted under the action of 1wt% CysH, but the elution performance for As is still weak. In 1wt% TU, all three elements were low except that Hg could be eluted in small amounts. EDTA eluents of different pH: the E9 has good elution performance on Cd and Pb, but has lower elution efficiency on As and Hg, the E12 has higher elution performance on Cd, pb, as, hg four heavy metals, the elution rate reaches more than 90%, the overall elution efficiency is reduced under the action of E14 with stronger alkalinity, and Pb is reduced to below 20%. The acidic eluent prepared from EDTA disodium has a certain eluting effect on Cd and Pb, but has unsatisfactory eluting performance on As and Hg. The elution performance of the other three elements is not ideal except that Hg has better elution effect under the alkaline elution environment of 0.1wt% NaOH. Thus, of the 8 eluents described above, the pH of 12, 1wt% EDTA solution E12 was finally determined as the optimal eluent.
Table 7 summary of adsorption experimental data
Example 5
The pretreatment method for applying the magnetic adsorption material m-P6 described in example 2 to rice flour comprises the following steps:
Adsorption/elution experiments on Cd and Pb: 0.2g of a rice flour sample containing a cadmium standard substance and a rice flour sample containing a lead standard substance (0.217 mg/kg of a cadmium standard substance, 0.221mg/kg of a lead standard substance, METAL-DJTZK-017, standard substances from national institute of food and materials science) were weighed and dispersed in 5% HNO, respectively 3 (v/v), centrifuging (8000 rpm) after swirling for 5min, pouring out supernatant, and adjusting pH to 5-9 with NaOH solution to obtain cadmium rice flour extract and lead rice flour extract. Subsequently, 50mg of the magnetic adsorption material m-P6 are respectively placed inAdsorbing the cadmium rice powder leaching solution and the lead rice powder leaching solution, swirling for 3min, and fixing m-P6 with strong magnet to pour out the leaching solution. Washing the adsorbed m-P6 with clear water for 2 times, placing in 5mL of EDTA solution E12 with pH of 12 and 1wt%, swirling for 5min, fixing m-P6 with strong magnet to obtain 0.5mL of clear solution, adding 4.5mL of 5% HNO 3 (v/v) dilution of the solution, and the adsorption concentration of m-P6 to Cd and Pb and the adsorption rate of rice flour heavy metal were determined by ICP-MS for the diluted sample, see Table 7, and the adsorption rate is Cd:95.9%, pd:89.1%.
Adsorption/elution experiments on As and Hg: 0.2g of rice flour sample (fixed value rice flour sample, arsenic content 0.200mg/kg, mercury content 0.046mg/kg, fixed value materials from national institute of food and materials and stock, national institute of research) was weighed, dispersed in 1wt.% CysH solution, centrifuged (8000 rpm) after 15 minutes by vortexing, the supernatant was decanted, and pH was adjusted to 5-9 with NaOH solution to obtain a leaching solution. Then, 50mg of the magnetic adsorption material m-P6 was placed in the leaching solution for adsorption, and after vortexing for 3min, the m-P6 was fixed by a strong magnet and the leaching solution was poured out. Washing the adsorbed m-P6 with clear water for 2 times, placing in 5mL EDTA solution E12 with pH of 12 and 1wt%, swirling for 5min, fixing m-P6 with strong magnet to obtain 0.5mL of clear solution, adding 4.5mL of 5% HNO 3 (v/v) dilution of the solution, and the adsorption concentration of m-P6 to As and Hg and the adsorption rate of rice flour heavy metals were measured by ICP-Mass for the diluted sample, see Table 7, and the adsorption rate was As:75.5%, hg:80.4%.
Table 8 summary of adsorption experimental data
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. A magnetically attractable material, the magnetically attractable material comprising
The crosslinking component consists of itaconic acid, acrylamide and N-allylthiourea;
the functional component consists of a cross-linking agent and an initiator;
and a magnetic component consisting of magnetic Fe 3 O 4 Particle composition;
the crosslinking component is crosslinked and embedded into the magnetic component under the action of the functional component;
wherein the mole ratio of itaconic acid to acrylamide to N-allylthiourea is 1-5:1:1;
The molar ratio of the crosslinking component, the crosslinking agent and the initiator is 3-7:0.3-2:0.002-0.02;
the molar ratio of the crosslinking component to the magnetic component is 3-7:0.3-1.5.
2. The magnetically attractable material of claim 1 wherein the molar ratio of itaconic acid, acrylamide and N-allylthiourea is 1:1:1;
the molar ratio of the crosslinking component, the crosslinking agent and the initiator is 3:2:0.02;
the molar ratio of the crosslinking component to the magnetic component is 3:1.
3. The magnetically attractable material of claim 1 wherein the crosslinker is selected from the group consisting of N, N' -methylenebisacrylamide;
preferably, the initiator comprises one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, ammonium persulfate, potassium persulfate, benzoyl peroxide and t-butyl benzoyl peroxide.
4. A method of preparing a magnetically attractable material according to any one of claims 1 to 3 comprising the steps of:
and in inert atmosphere, adding the crosslinking component, the magnetic component and the crosslinking agent in proportion, then adding the solvent, stirring uniformly, adding the initiator, heating to the reaction temperature for reaction, and washing and drying after the reaction is finished to obtain the magnetic adsorption material.
5. The method according to claim 4, wherein the reaction temperature is 60-80 ℃ and the reaction time is 6-24 hours.
6. A heavy metal enrichment kit, characterized in that the heavy metal enrichment kit comprises:
a magnetically attractable material as claimed in any one of claims 1 to 3 or as prepared by a method as claimed in any one of claims 4 to 5.
7. The heavy metal enrichment kit of claim 6, further comprising an eluent;
the eluent comprises one or more of nitric acid solution, cysteine hydrochloride solution, thiourea solution, EDTA disodium solution, naOH solution and EDTA alkali solution;
preferably, the eluent is selected from EDTA base solution;
preferably, the eluent is selected from EDTA alkaline solutions having a pH of 12, 1 wt%.
8. The pretreatment method for detecting the heavy metal content in the grains is characterized by comprising the following steps of:
dispersing heavy metal-containing grains in dilute acid solution or cysteine hydrochloride solution by using the kit as claimed in any one of claims 6 to 7, and vortex to obtain leaching solution;
adsorbing heavy metal ions in the leaching solution by using a magnetic adsorption material, and vortex to obtain the magnetic adsorption material enriched with the heavy metal ions;
Eluting and magnetically separating the magnetic adsorption material enriched with heavy metal ions to obtain an enriched treatment solution containing heavy metal ions;
preferably, the adsorption time is 1-30min, and the elution time is 1-30min;
preferably, the adsorption time is 3-15min, and the elution time is 5-10min.
9. The pretreatment method according to claim 8, wherein the heavy metal ion includes Cd 2+ 、Pb 2+ 、As 3+ And Hg of 2+ One or more of the following.
10. The heavy metal enrichment and purification method is characterized by comprising the following steps of:
the kit according to claim 6 is used, the magnetic adsorption material is added into a solution containing heavy metal ions for adsorption, and the magnetic adsorption material with the heavy metal ions adsorbed is taken out after the adsorption is finished, so that purified supernatant is obtained.
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