CN115532235A - Lanthanum-based adsorbent and preparation method and application thereof - Google Patents
Lanthanum-based adsorbent and preparation method and application thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 80
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 68
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 25
- RHXSYTACTOMVLJ-UHFFFAOYSA-N 1H-benzimidazole-2-carboxylic acid Chemical class C1=CC=C2NC(C(=O)O)=NC2=C1 RHXSYTACTOMVLJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims abstract description 7
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims abstract description 7
- IGBVGUDGCXLPHR-UHFFFAOYSA-N C1=CC=C2N(CC(O)=O)C(C)N(CC(O)=O)C2=C1 Chemical group C1=CC=C2N(CC(O)=O)C(C)N(CC(O)=O)C2=C1 IGBVGUDGCXLPHR-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 239000002594 sorbent Substances 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 150000004715 keto acids Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical class O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 47
- 239000011259 mixed solution Substances 0.000 abstract description 20
- 239000010452 phosphate Substances 0.000 abstract description 9
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 21
- -1 lanthanum carbonate hydroxide phosphate Chemical compound 0.000 description 18
- 239000000356 contaminant Substances 0.000 description 13
- 239000003344 environmental pollutant Substances 0.000 description 13
- 231100000719 pollutant Toxicity 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000013110 organic ligand Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000001048 orange dye Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010060860 Neurological symptom Diseases 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- TXTQARDVRPFFHL-UHFFFAOYSA-N [Sb].[H][H] Chemical compound [Sb].[H][H] TXTQARDVRPFFHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000037380 skin damage Effects 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a lanthanum-based adsorbent and a preparation method and application thereof, and the lanthanum-based adsorbent is a complex formed by benzimidazole carboxylic acid derivatives and lanthanum salt, wherein the lanthanum salt comprises lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate and lanthanum hydroxide. The maximum adsorption capacity of the lanthanum-based adsorbent prepared by the invention to antimonate (Sb (V)), phosphate (P (V)), arsenite (As (III)), arsenite (As (V)) and antimonite (Sb (III)) is 896.5mg/g, 426.9mg/g, 271.7mg/g, 154.6mg/g and 91.5mg/g respectively; at 15min, the removal rates of Sb (V), P (V), as (III), as (V) and Sb (III) by the La-MGs are 97.8%, 97.0%, 87.3%, 79.3% and 80.4% respectively; the utilization rate of Sb (V) on the surface of the adsorbent reaches 50.1 percent, and the adsorbent has higher utilization rate of Sb (V) on the surface of the adsorbent. In addition, in the mixed solution, la-MGs have better selection performance to Sb (V).
Description
Technical Field
The invention relates to the field of heavy metal adsorbents, in particular to a lanthanum-based adsorbent and a preparation method and application thereof.
Background
The contamination with oxygen-containing acids in aqueous solutions, in particular arsenite (As (III)) and antimony (Sb (III)), has attracted global attention because of their high toxicity and carcinogenicity, which pose a great threat to human health even at low concentrations. Drinking water is considered to be the primary route for the contamination of oxygenates such as arsenic (III) and antimony (III), which can cause serious health problems such as skin damage, neurological symptoms and even cancer, a feature that requires effective removal. Adsorption technology is considered to be an efficient, simple technology, which is more efficient than other technologies. However, targeted removal of a particular contaminant in a solution is difficult due to the varying degree of matching between the adsorbent and the different contaminants.
In recent years, efforts have been made to design and construct reasonable adsorption structures to improve the adsorption performance for target pollutants. Advanced functional materials such as metal oxides, metal-organic frameworks, biomass-based materials, and covalent organic frameworks have all been used to explore the relationship between adsorption configuration and contaminant removal performance. Research shows that UiO-66-SH-A with higher lattice defect forms stable adsorption configuration, so that the adsorption capacity to As (III)/As (V) is higher and the speed is faster. In addition, MOF UiO-66-3C4N showed strong uranyl adsorption capacity in both simulated and natural seawater, mainly due to the smaller nanocapsules increasing the coordination between the adsorbent and the uranium. To date, exploring the impact of degree of matching on the adsorption performance of contaminants on adsorbents remains a significant challenge and few have been studied.
Chinese patent publication No. CN113019305B discloses preparation of porous lanthanum carbonate hydroxide phosphate adsorbent and its application. Wherein the preparation comprises: and carrying out hydrothermal reaction on the mixed solution of lanthanum chloride, urea and sodium citrate at 120-180 ℃ to obtain the adsorbent. The adsorbent disclosed by the invention has the advantages of higher adsorption rate, higher adsorption capacity and selectivity for phosphate, and good regeneration and recycling performance.
The Chinese patent with publication number CN103240060A designs and synthesizes a novel metal organic gel, which is a gel formed by binding small solvent molecules by forming a complex by benzimidazole carboxylic acid derivatives and metal lead ions. SEM results show that the metal organogel presents an interwoven three-dimensional network structure. The adsorption experiment of methyl orange dye molecules shows that the metal organogel can efficiently and selectively adsorb the methyl orange molecules in a water phase, so that the metal organogel is a novel material for treating water polluted by the methyl orange dye molecules.
The Chinese patent with the publication number of CN113019305B uses lanthanum chloride to prepare the adsorbent, has a fast adsorption rate on phosphate, and the Chinese patent with the publication number of CN103240060A uses benzimidazole carboxylic acid derivatives to prepare metal organic gel for treating methyl orange dye molecule polluted water. At present, no technology is available for removing the oxygen acid radical ion pollution in water by using lanthanum chloride and benzimidazole carboxylic acid derivatives.
Disclosure of Invention
The invention aims to solve the technical problem that aiming at the defects of the prior art, the invention provides the lanthanum-based adsorbent and the preparation method thereof, which can efficiently and quickly capture antimonate in sewage, and simultaneously, phosphate radicals in the sewage have small influence on antimonate removal.
The invention also provides application of the lanthanum-based adsorbent in targeted removal of antimonate from oxygen acid radicals.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a lanthanum-based adsorbent is a complex of benzimidazole carboxylic acid derivatives and lanthanum salts, including lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate and lanthanum hydroxide.
The lanthanum-based adsorbent synthesized by the method has different matching degrees with different pollutants, so that the coordination action force between the adsorbent and the pollutants is different, and the adsorption performance of the material is influenced. Compared with the prior art, the lanthanum-based adsorbent synthesized by the method can efficiently and quickly capture oxygen-containing acid radicals, particularly antimonate radicals, and the influence of phosphate radicals in a mixed solution on the removal of the antimonate radicals is small. Thus, lanthanum-based adsorbents are a novel material for the treatment of oxygenate-contaminated water.
In a preferred embodiment of the invention, the benzimidazole carboxylic acid derivative is 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG) and the lanthanum salt is lanthanum chloride heptahydrate.
In the experiment, 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG) and lanthanum salt formed lanthanum-based adsorbent La-MGs have better adsorption performance on Sb (V) than 2-Methylbenzimidazole (MC) and lanthanum salt formed lanthanum-based adsorbent La-MCs. The lanthanum-based adsorbent synthesized by using 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG) as an organic ligand has a porous structure, and can efficiently, quickly and selectively capture antimonate in a mixed solution, so that the selective removal of oxygen-containing acid radicals in wastewater is realized. In the formed lanthanum-based adsorbent La-MGs, when the anions are lanthanum chloride, the adsorption performance of the lanthanum-based adsorbent on Sb (V) is better than that of the lanthanum-based adsorbent of which the anions are lanthanum nitrate hexahydrate and lanthanum hydroxide in sequence.
In a preferred embodiment of the present invention, the molar ratio of the benzimidazole carboxylic acid derivative to the lanthanum chloride is 1.25 to 5mmol: 2.5-10 mmol. Further preferably, the molar ratio of the benzimidazole carboxylic acid derivative to the lanthanum chloride is 1.25 to 5mmol: 2.5-5 mmol.
The invention also discloses a preparation method of the lanthanum-based adsorbent, which comprises the following steps:
s1, dissolving lanthanum salt in a solvent to form a lanthanum salt solution;
and S2, adding benzimidazole carboxylic acid derivatives into the lanthanum salt solution of the S1, uniformly mixing, heating and drying, and obtaining the lanthanum-based adsorbent after the reaction is finished.
In a preferred embodiment of the invention, the temperature for heating and drying in S2 is 120-180 ℃ and the time is 8-24 h. The adsorption performance of the material can be different due to different time and temperature, and the temperature and the time are selected to ensure that the material obtains the maximum adsorption quantity. The formed morphology structure is a porous structure stacked by nano sheets, and the morphology is obviously changed after different pollutants are adsorbed.
In a preferred embodiment of the invention, the benzimidazole carboxylic acid derivative is 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG) and the lanthanum salt is lanthanum chloride heptahydrate.
In a preferred embodiment of the present invention, the molar ratio of the benzimidazole carboxylic acid derivative to the lanthanum salt is 1.25 to 5mmol: 2.5-10 mmol.
In a preferred embodiment of the present invention, the solvent in S1 is water, methanol and absolute ethanol; preferably, the solvent in S1 is absolute ethanol.
The molar volume ratio of the benzimidazole carboxylic acid derivative to the lanthanum salt to the absolute ethyl alcohol is 1.25-5 mmol: 2.5-10 mmol:30-60mL.
The mixing mode in the S2 is ultrasonic mixing for 30-60 min.
The invention also discloses an application of the lanthanum-based adsorbent in targeted removal of the oxygen-containing acid radicals in sewage.
In a preferred embodiment of the invention, the sewage comprises oxygen-containing acid radicals and other heavy metal ions, the oxygen-containing acid radicals comprise antimonite (Sb (V)), phosphate (P (V)), arsenite (As (III)), arsenite (As (V)) and antimonite (Sb (III)), and the targeted removal of the oxygen-containing acid radicals is not influenced by phosphate, nitrate and sulfate in the sewage; preferably, the targeted removal of the oxo acid is antimonate (Sb (V)).
Compared with the prior art, the invention has the following beneficial effects: the invention regulates and controls the coordination acting force of the pollutants and the adsorption sites by changing the matching degree of the pollutants and the adsorbent, thereby influencing the removal performance of the pollutants on the surface of the adsorption material. The maximum adsorption capacity of the lanthanum-based adsorbent prepared by the invention to antimonate (Sb (V)), phosphate (P (V)), arsenite (As (III)), arsenite (As (V)) and antimonite (Sb (III)) is 896.5mg/g, 426.9mg/g, 271.7mg/g, 154.6mg/g and 91.5mg/g respectively; at 15min, the removal rates of Sb (V), P (V), as (III), as (V) and Sb (III) by the La-MGs are 97.8%, 97.0%, 87.3%, 79.3% and 80.4% respectively; the utilization rate of Sb (V) on the surface of the adsorbent reaches 50.1 percent, and the adsorbent has higher utilization rate of Sb (V) on the surface of the adsorbent. In addition, in the mixed solution, la-MGs have better selection performance to Sb (V). The work discusses the influence of the local coordination environment of the adsorption sites on the adsorption performance from the aspect of removing objects, and provides a new idea for the selective and efficient adsorption of pollutants.
Drawings
FIG. 1 shows the adsorption performance of lanthanum-based adsorbents for two ligands on Sb (V);
FIG. 2 shows the adsorption performance of three different anionic lanthanum-based adsorbents on Sb (V);
FIG. 3 shows the adsorption performance of lanthanum-based adsorbents on Sb (V) obtained in three different solvents;
FIG. 4 shows the adsorption performance of a lanthanum-based adsorbent on Sb (V) obtained by the ratio of metal ions to organic ligands;
FIG. 5 morphology change before and after lanthanum-based sorbent captures different contaminants;
FIG. 6Sb (V) adsorption performance on lanthanum-based adsorbents;
fig. 7P (V) adsorption performance on lanthanum-based adsorbents;
FIG. 8 shows the adsorption performance of As (III) on a lanthanum-based adsorbent;
FIG. 9 shows the adsorption performance of As (V) on a lanthanum-based adsorbent;
fig. 10Sb (III) adsorption performance on lanthanum-based adsorbents;
FIG. 11 selectivity experiments for La-MGs at low concentrations. C Sb(V) =2mm, v =50ml, adsorbent dose =1.0g/L, pH =3, t =24h, t =25 ℃.
Detailed Description
Example 1
The lanthanum-based adsorbent in this example is prepared by using 1,3-dicarboxymethyl-2-methylbenzimidazole as an organic ligand, lanthanum chloride heptahydrate as a metal center, water, methanol and absolute ethanol as solvents, and adopting a solvothermal method.
(1) Mixing metal salts of lanthanum chloride heptahydrate, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol, and ultrasonically mixing uniformly for 30min to obtain a mixed solution; wherein the molar volume ratio of the metal salt lanthanum chloride heptahydrate, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol is 8mmol.
(2) And (2) placing the mixed solution obtained in the step (1) in an oven for reaction at the temperature of 120 ℃ for 12 hours to obtain the lanthanum-based adsorbent La-MGs.
Example 2
(1) Mixing metal salt lanthanum chloride heptahydrate, 2-Methylbenzimidazole (MC) and absolute ethyl alcohol, and ultrasonically mixing uniformly for 30min to obtain a mixed solution; wherein the molar volume ratio of the metal salt lanthanum chloride heptahydrate, 2-Methylbenzimidazole (MC) and absolute ethyl alcohol is 8mmol.
(2) And (2) placing the mixed solution obtained in the step (1) in an oven for reaction at the temperature of 120 ℃ for 12 hours to obtain the lanthanum-based adsorbent La-MCs.
Lanthanum-based adsorbents were prepared from the organic ligands 2-Methylbenzimidazole (MC) and 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG) and the metal salt lanthanum chloride heptahydrate, respectively. As shown in FIG. 1, 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG) and lanthanum salt formed lanthanum-based adsorbent La-MGs have been found to have better adsorption performance on Sb (V) than 2-Methylbenzimidazole (MC) and lanthanum salt formed lanthanum-based adsorbent La-MCs. The lanthanum-based adsorbent synthesized by using 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG) as an organic ligand has a porous structure and can efficiently, quickly and selectively capture antimonate in a mixed solution, so that the selective removal of oxygen-containing acid radicals in wastewater is realized.
Example 3
(1) Mixing lanthanum salt, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol, and ultrasonically mixing uniformly for 45min to obtain a mixed solution; wherein the molar volume ratio of the lanthanum salt, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol is 8mmol. Wherein the lanthanum salt is lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate and lanthanum hydroxide respectively.
(2) Placing the mixed solution obtained in the step (1) in an oven for reaction at the temperature of 120 ℃ for 12 hours to respectively prepare white powder solid LaCl with anions of lanthanum chloride, lanthanum nitrate hexahydrate and lanthanum hydroxide 3 -MGs, light yellow powdery solid La (NO) 3 ) 3 MGs and white lump estimation La (OH) 3 -MGs。
In the lanthanum-based adsorbent La-MGs formed as shown in FIG. 2, the adsorption performance of lanthanum chloride as an anion on Sb (V) is better than that of lanthanum nitrate hexahydrate and lanthanum hydroxide in sequence.
Example 4
(1) Mixing metal salt lanthanum chloride heptahydrate and 1,3-dicarboxymethyl-2-methylbenzimidazole with a solvent, and ultrasonically mixing uniformly for 30min to obtain a mixed solution; wherein the molar volume ratio of the metal salt lanthanum chloride heptahydrate, 1,3-dicarboxymethyl-2-methylbenzimidazole and the solvent is 8mmol. Wherein the solvent is selected from water, methanol and absolute ethyl alcohol.
(2) And (2) placing the mixed solution obtained in the step (1) in an oven for reaction at the temperature of 120 ℃ for 12 hours to obtain the lanthanum-based adsorbent La-MGs.
As shown in fig. 3, among the adsorption performances of the lanthanum-based adsorbents obtained in three different solvents on Sb (V), the adsorption performance of the lanthanum-based adsorbents La-MGs prepared from anhydrous ethanol on Sb (V) is the best.
Example 5
(1) Mixing metal salts of lanthanum chloride heptahydrate, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol, and ultrasonically mixing uniformly for 30min to obtain a mixed solution; the volume of the absolute ethyl alcohol is 40mL, and the proportion of the metal salt lanthanum chloride heptahydrate and 1,3-dicarboxymethyl-2-methylbenzimidazole is respectively 0.5.
(2) And (2) placing the mixed solution obtained in the step (1) in an oven for reaction at the temperature of 120 ℃ for 12 hours to obtain the lanthanum-based adsorbent La-MGs.
Fig. 4 shows the adsorption performance of the lanthanum-based adsorbent on Sb (V) obtained by the ratio of metal ions to organic ligands, and when the ratio of the metal salt lanthanum chloride heptahydrate to 1,3-dicarboxymethyl-2-methylbenzimidazole is 2:1, the obtained lanthanum-based adsorbent has the best adsorption performance on Sb (V). Therefore, the preferable proportion range of the metal salt lanthanum chloride heptahydrate and 1,3-dicarboxymethyl-2-methylbenzimidazole is 1:1-2:1.
Example 6
(1) Mixing metal salt lanthanum chloride heptahydrate, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol, and performing ultrasonic mixing for 30min to obtain a mixed solution; wherein the molar volume ratio of the metal salt lanthanum chloride heptahydrate, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol is 8mmol.
(2) And (2) placing the mixed solution obtained in the step (1) in an oven for reaction at the temperature of 120 ℃ for 8 hours to obtain the lanthanum-based adsorbent La-MGs.
Example 7
(1) Mixing metal salts of lanthanum chloride heptahydrate, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol, and ultrasonically mixing uniformly for 30min to obtain a mixed solution; wherein the molar volume ratio of the metal salt lanthanum chloride heptahydrate, 1,3-dicarboxymethyl-2-methylbenzimidazole and absolute ethyl alcohol is 8mmol.
(2) And (2) placing the mixed solution obtained in the step (1) in an oven for reaction at the temperature of 180 ℃ for 24 hours to obtain the lanthanum-based adsorbent La-MGs.
The lanthanum-based adsorbent obtained in example 1 was added to a solution of five contaminants at an initial concentration of 1g/L (initial concentration of five contaminants) for reaction for 24 hours, and then the residual concentrations of the species contaminants in the solution were measured to obtain lanthanum-based adsorbents having adsorption amounts of five contaminants (Sb (V), P (V), as (III), as (V), and Sb (III)) of 896.5mg/g, 426.9mg/g, 271.7mg/g, 154.6mg/g, and 91.5mg/g in this order, as shown in fig. 6 to 10. Fig. 5 shows the morphology change before and after the lanthanum-based adsorbent captures different pollutants, the formed morphology structure is a porous structure stacked by nanosheets, and the morphology changes obviously after the lanthanum-based adsorbent adsorbs different pollutants.
Application example 1
An initial Sb (V) solution was prepared at a concentration of 2mM by adding a predetermined amount of F to the test solution - ，NO 3 - ，H 2 PO 4 - ，AsO 2 - ，SbO 2 - 、SO 4 2- And AsO 4 2- 50mL of the lanthanum-based adsorbent prepared in example 1 is added into a conical flask, 50mg of the lanthanum-based adsorbent is added into the conical flask, the mixture is placed into a constant-temperature shaking box at 25 ℃ and 180r/min for reaction for 24 hours, and the conical flask is taken out and filtered through a 0.45um filter membrane for later use. The concentration of As remaining in the solution was measured by ICP, the concentration of Sb remaining in the solution was measured by atomic absorption Spectroscopy, and P (V) and F remaining in the solution were measured - 、NO 3 - 、Cl - And SO 4 2- Ion for concentrationAnd (5) detecting by chromatography.
Sb(V)、P(V)、As(III)、As(V)、Sb(III)、F - 、NO 3 - 、Cl - And SO 4 2- Adsorption capacity (Q) of e ) The calculation of (c) follows the following formula:
in the formula: c 0 Concentrations of different contaminants in the initial solution (mg/L); c e Concentration of different pollutants in the solution after adsorption (mg/L); q e Adsorption capacity (mg/g) for lanthanum-based adsorbents for different contaminant concentrations; v is the volume (mL) of the solution to be adsorbed in the flask; and m is the mass (mg) of the added lanthanum-based adsorbent.
According to the formula, the adsorption performance of the lanthanum-based adsorbent pair can be calculated when the solution concentration is 2mM for different pollutants, and the specific result is shown in FIG. 11. The target removal process of antimonate (Sb (V)) is not influenced by phosphate radical, nitrate radical and sulfate radical in the sewage. The selection experiment shows that the lanthanum-based adsorbent has good selectivity on Sb (V) and can selectively capture the Sb (V) from eight pollutants. The site utilization of different contaminants adsorbed on La-MGs is shown in Table 1, wherein the utilization of the adsorption site of Sb (V) is 50.1%.
TABLE 1 utilization of sites of adsorption of different contaminants onto La-MGs
a the total amount of adsorption sites in the La-MGs adsorbent was 8mM.
Claims (10)
1. A lanthanum-based adsorbent characterized by being a complex of a benzimidazole carboxylic acid derivative and a lanthanum salt, the lanthanum salt comprising lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate, and lanthanum hydroxide.
2. The lanthanum-based sorbent of claim 1, wherein the benzimidazole carboxylic acid derivative is 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG) and the lanthanum salt is lanthanum chloride heptahydrate.
3. The lanthanum-based sorbent according to claim 1, wherein the molar ratio of the benzimidazole carboxylic acid derivative to the lanthanum chloride is 1.25 to 5mmol: 2.5-10 mmol.
4. A preparation method of a lanthanum-based adsorbent is characterized by comprising the following steps:
s1, dissolving lanthanum salt in a solvent to form a lanthanum salt solution;
and S2, adding benzimidazole carboxylic acid derivatives into the lanthanum salt solution of the S1, uniformly mixing, heating and drying, and obtaining the lanthanum-based adsorbent after the reaction is finished.
5. The method for preparing a lanthanum-based adsorbent according to claim 4, wherein the temperature for heating and drying in S2 is 120 ℃ to 180 ℃ for 8 to 24 hours.
6. The method of claim 4, wherein the benzimidazole carboxylic acid derivative is 1,3-dicarboxymethyl-2-Methylbenzimidazole (MG), and the lanthanum salt is lanthanum chloride heptahydrate.
7. The method of preparing a lanthanum-based sorbent according to claim 4, wherein the molar ratio of the benzimidazole carboxylic acid derivative to the lanthanum salt is 1.25 to 5mmol: 2.5-10 mmol.
8. The method for producing a lanthanum-based adsorbent according to claim 4, wherein the solvent in S1 is water, methanol, and absolute ethanol; preferably, the solvent in S1 is absolute ethanol.
9. Use of a lanthanum-based sorbent according to any of claims 1 to 3 for the targeted removal of oxygenates from wastewater.
10. The use of the lanthanum-based sorbent for the targeted removal of oxygenates in wastewater according to claim 9, characterized in that oxygenates and other heavy metal ions are included in the wastewater, the oxygenates include antimonates (Sb (V)), phosphates (P (V)), arsenites (As (III)), arsenates (As (V)) and antimonites (Sb (III)), and the targeted removal of the oxygenates is not affected by phosphates, nitrates, sulfates in the wastewater; preferably, the targeted removal of the oxo acid is antimonate (Sb (V)).
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