CN112551674B - Method for removing aromatic sulfonic acid anions in aqueous solution and aromatic sulfonic acid anion CMOFs material - Google Patents

Method for removing aromatic sulfonic acid anions in aqueous solution and aromatic sulfonic acid anion CMOFs material Download PDF

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CN112551674B
CN112551674B CN202011463232.2A CN202011463232A CN112551674B CN 112551674 B CN112551674 B CN 112551674B CN 202011463232 A CN202011463232 A CN 202011463232A CN 112551674 B CN112551674 B CN 112551674B
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李生华
彭盼盼
庞思平
弥永胜
赵超峰
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Beijing Institute of Technology BIT
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
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Abstract

The invention relates to a method for removing aromatic sulfonic acid anions in an aqueous solution and a CMOFs material containing the aromatic sulfonic acid anions, belonging to the field of sewage treatment. According to the method, an ATRZ aqueous solution and an inorganic metal salt aqueous solution are dropwise added into a sewage solution containing aromatic sulfonate anions, and a high-crystalline and water-insoluble CMOFs crystal taking the aromatic sulfonate anions as balance anions is formed by means of coordination interaction, so that the aromatic sulfonate anions in the aqueous solution are effectively removed. The method is simple to operate, mild in condition, suitable for aromatic sulfonate anions containing different groups and high in selectivity.

Description

Method for removing aromatic sulfonic acid anions in aqueous solution and aromatic sulfonic acid anion CMOFs material
Technical Field
The invention relates to a method for removing aromatic sulfonic acid anions in an aqueous solution and a CMOFs material containing the aromatic sulfonic acid anions, belonging to the field of sewage treatment.
Background
The aromatic sulfonate is mainly an organic aromatic compound which mainly comprises benzene sulfonic acid (sodium and potassium) salt and homologues thereof. Since the introduction of different functional groups can further expand the structure and adjust the properties of the aromatic sulfonate, most of the common aromatic sulfonates have different modifying groups (such as 4-methylbenzene)Sodium sulfonate, sodium 2-iodobenzene sulfonate, and the like). A great deal of related documents already show that the modified aromatic sulfonic acid anion has unique properties, so that the aromatic sulfonic acid salt has a wide application range and is applied to the fields of medicines, catalysis, pesticides, nonlinear optical materials, dyes (such as methyl orange and acid red 88), energetic materials, ionic liquids and the like. For example, sulfonate anions (TS)-) The derivative has special biological characteristics and is widely existed in active drug salts such as lapatin (GW-572016) diglycoside, potassium benzene sulfonate, sorafenib tosylate and the like. However, the aromatic sulfonate anion, as a derivative of the benzene compound, has certain toxicity and great harm to human bodies, and can cause serious eye irritation and skin and respiratory tract irritation, influence the activity of enzymes and disturb the physiological metabolism of human beings. In addition, if the waste liquid containing the aromatic sulfonate anions is directly discharged, the natural biochemical degradation of the aromatic sulfonate anions is difficult, so that the pollution of water resources can be caused, and the aromatic sulfonate anions can also perform exchange reaction with ions in soil, so that the physical and chemical properties of the soil are changed, and the normal physical and chemical functions of the soil are influenced.
Cationic Metal Organic Frameworks (CMOFs) are an important class of framework materials. It is formed by the coordination of neutral organic ligand and metal ion to form cation skeleton, the pore channel of which is occupied by balancing anion, such as Cl-、NO3 -、ClO4 -And BF4 -Etc., anions located in the framework structure can exist freely in the cavities or have weak interactions with the host framework. This structure can be selected and designed for its own accord, while having a visible spatial structure. There is currently no report of the use of CMOFs to remove aromatic sulfonate anions by construction.
Disclosure of Invention
In view of the above, the present invention provides a method for removing aromatic sulfonate anions from an aqueous solution and an aromatic sulfonate anion CMOFs material, in which aromatic sulfonate anions are fixed in channels of the CMOFs to remove the aromatic sulfonate anions from the aqueous solution, and the method is simple to operate, mild in conditions, suitable for aromatic sulfonate anions containing different groups, and high in selectivity.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for removing aromatic sulfonic acid anions from an aqueous solution, the method comprising the steps of:
adjusting the pH value of an aromatic sulfonate anion-containing aqueous solution to 5-7, filtering to obtain a clear solution, adding 4, 4' -azo-1, 2,4-triazole (ATRZ, molecule C) into the clear solution4H4N8Nitrogen content of 68.4%) and inorganic metal salt aqueous solution, stirring for 10-30 min at 20-30 ℃, filtering after stirring, standing the obtained filtrate until crystals are completely separated out, and filtering to obtain a solution for removing aromatic sulfonic acid anions;
wherein the molar ratio of ATRZ, aromatic sulfonate and inorganic metal salt is 3:1.5: 3-3: 2.5: 3;
the inorganic metal salt is copper salt, cobalt salt or ferrous salt;
when the inorganic metal salt is a copper salt, the aromatic sulfonate anion is 4-methylbenzenesulfonate ion (TS)-) 4-Aminobenzenesulphonic acid ion (ABS)-) 2-iodobenzene sulfonate Ion (IBS)-) 4-Nitrobenzenesulfonic acid ion (NBS)-) 2, 4-dinitrobenzene sulfonic acid ion (DNBS)-) 2, 5-Dihydroxybenzenesulfonic acid ion (DHBS)-) 2,3,5, 6-tetrafluoro-4-hydroxybenzenesulfonic acid ion (TFHBS)-) 2,4, 6-Trimethylbenzenesulfonic acid ion (TTBS)-) 1, 3-benzenedisulfonic acid ion (BDS)-) 2-naphthalenesulfonic acid ion (NTS)-) 6-hydroxy-2-naphthalenesulfonic acid ion (HNTS)-) One or more of (1); when the inorganic metal salt is a cobalt salt, the skeleton balancing anion is 4-acetophenone benzene sulfonic acid ion (AABS)-) And/or 2-aldehyde benzenesulfonic acid ion (FBS)-) (ii) a When the inorganic metal salt is an iron salt, the backbone-balancing anion is 4-methylbenzenesulfonic acid ion (TS)-) And/or 2, 4-dinitrobenzene sulfonate ion (DNBS)-)。
Preferably, the conditioning with an acid solution or an alkali solutionpH of aqueous solution of aromatic sulfonate anion, the acid being HCl, H2SO4And HNO3The alkali is KOH, NaOH or Na2CO3And NaHCO3More than one of them.
Preferably, the alkali is NaOH and NaHCO at the mass ratio of 1:23Or the alkali is KOH and KHCO with the mass ratio of 1:23。
Preferably, the ATRZ aqueous solution is added first, and then the aqueous inorganic metal salt solution is added.
Preferably, the copper salt is Cu (NO)3)2、CuSO4、Cu(BF4)2、Cu(ClO4)2、CuBr2And CuCl2More than one of them.
Preferably, the cobalt salt is Co (NO)3)2、CoCl2、Co(ClO4)2And Co (BF)4)2More than one of them.
Preferably, the iron salt is FeSO4、Fe(NO3)2And FeCl2More than one of them.
Preferably, the standing time is 3-7 days.
The CMOFs material is obtained by washing crystals after filtration by the method and drying the crystals in vacuum, and is composed of coordination metal cations, neutral organic ligands and framework balance anions, wherein the coordination metal cations are transition metal copper ions, cobalt ions, zinc ions or iron ions, the neutral organic ligands are energetic organic ligands ATRZ with high nitrogen content, and the framework balance anions are aromatic sulfonic acid anions.
When the metal cation is copper ion, the skeleton balancing anion is TS-、ABS-、IBS-、NBS-、DNBS-、DHBS-、TFHBS-、TTBS-、BDS-、NTS-And HNTS-One or more of (1); when the metal cation is cobalt ion, the skeleton balancing anion is AABS-And/or FBS-(ii) a When the metal cation is iron ion, the skeleton balancing anion is TS-And/or DNBS-。
Preferably, the drying temperature is 50-80 ℃, and the drying time is 5-7 h.
Advantageous effects
(1) According to the invention, through an improved inorganic-organic mixed anion method, aromatic sulfonate anions are successfully fixed in cavities of the CMOFs in a balanced anion mode, so that not only is the removal of aromatic sulfonate ions in an aqueous solution successfully realized, but also a novel heterocyclic anion type CMOFs material is successfully obtained.
(2) The method disclosed by the invention is simple to operate, mild in reaction condition, suitable for various different metal ions and aromatic sulfonate anions, and simple in representation of the removal effect of the aromatic sulfonate anions.
(3) The method has good removal effect, and can keep strong selectivity for removing aromatic sulfonate anions when the method coexists with various different inorganic anions.
Drawings
FIG. 1 shows the results of IR spectroscopy measurements of CMOFs crystals as described in example 1;
FIG. 2 is a powder X-ray diffraction (XRD) test result of the CMOFs crystal of example 2;
FIG. 3 is a diagram of the coordination environment of the CMOFs crystals of examples 1-11;
FIG. 4 is a packing diagram of crystals of CMOFs described in examples 1-11;
FIG. 5 is a diagram of the coordination environment of the CMOFs crystals of examples 12-13;
FIG. 6 is a packing diagram of the crystals of CMOFs described in examples 12-13;
FIG. 7 is a diagram of the coordination environment of the CMOFs crystals of examples 14-15;
FIG. 8 is a stacked view of the CMOFs crystals of examples 14-15.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the following examples:
(1) the synthesis of ATRZ was carried out according to the method described in "Li S H, Pang S P, Li X T, et al.Synthesis of new tetrazene (N-N ═ N-N) -linked bi (1,2, 4-triazine) [ J ]. Kunststoff-Kagaku (English edition), 2007, 18(10): 1176-.
(2) The aromatic sulfonic acid sodium salts (all from carbofuran reagent company, purity 98%, obtained by direct purchase) were used, and the structural formula of the aromatic sulfonate anion is shown below:
Figure BDA0002833377640000051
example 1
A method for removing aromatic sulfonate anions from an aqueous solution, the method comprising the steps of:
(1) pretreatment of laboratory waste liquid containing aromatic sulfonate anions: dropwise adding nitric acid and sodium hydroxide solution into chemical waste liquid containing aromatic sulfonate anions, chloride ions, bromide ions, sulfate radicals, nitrate radicals and perchlorate radicals, adjusting the pH of the system to be 5-7, and filtering to obtain clear waste liquid without solid impurities; wherein the aromatic sulfonate is 4-methyl benzene sulfonic acid sodium salt (NaTS);
(2) a solution of ATRZ (0.492g, 3.0mmol) in 10mL of H2In O, obtain an aqueous ATRZ solution, and dissolve inorganic copper metal salt (3.0mmol) in 10mL of H2O to obtain inorganic metal salt solution; wherein the inorganic metal salt is Cu (NO)3)2；
(3) And (2) sequentially adding an ATRZ aqueous solution and an inorganic metal salt solution into 5mL of the waste liquid obtained in the step (1), stirring for 20min at 20 ℃, filtering, standing the obtained clear liquid for 30min at room temperature, starting crystal precipitation in the mother liquid, continuously standing for 3 days until no crystal precipitation exists in the solution, performing suction filtration on the solution, washing with 5mL of water for 3 times, and performing vacuum drying at 65 ℃ for 7h to obtain a solid, namely a CMOFs crystal MOF (CuTS) taking aromatic sulfonate anions as balance anions, wherein the obtained clear solution is the solution after the aromatic sulfonate anions are removed.
The aromatic sulfonate anion removal efficiency was 75.49%.
The crystal structure parameters of the mof (cuts) are shown in table 1.
After standing for different times, the infrared spectrum result of the CMOFs crystal is shown in figure 1, the powder XRD result of the CMOFs crystal is shown in figure 2, and the result shows that only aromatic sulfonate anions exist in the crystal but no inorganic anions exist, which indicates that the method has strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 2
In this embodiment, the aromatic sulfonate is 2-iodobenzene sulfonic acid sodium salt (NaIBS), and the inorganic metal salt is CuSO4The CMOFs crystals are mof (cuibs), as in example 1.
The aromatic sulfonate anion removal efficiency was 76.19%.
The crystal structure parameters of the mof (cuibs) are shown in table 1.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 3
In this embodiment, the aromatic sulfonic acid salt is 4-aminobenzenesulfonic acid sodium salt (NaABS), and the inorganic metal salt is Cu (BF)4)2The CMOFs crystals are mof (cuabs), otherwise as in example 1.
The aromatic sulfonate anion removal efficiency was 78.31%.
The crystal structure parameters of the mof (cuabs) are shown in table 1.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 4
In this example, the aromatic sulfonic acid salt was 4-nitrobenzenesulfonic acid sodium salt (NaNBS), and the inorganic metal salt was Cu (ClO)4)2The CMOFs crystals are mof (cunbs), otherwise as in example 1.
The aromatic sulfonate anion removal efficiency was 75.22%.
The crystal structure parameters of the mof (cunbs) are shown in table 2.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 5
In this example, the aromatic sulfonate is 2, 4-dinitrobenzenesulfonic acid sodium salt (NaDNBS), and the inorganic metal salt is CuBr2The CMOFs crystals are mof (cudnbs) and the rest is as in example 1.
The aromatic sulfonate anion removal efficiency was 76.51%.
The crystal structure parameters of the mof (cudnbs) are shown in table 2.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 6
In this example, the aromatic sulfonate is 2, 5-dihydroxybenzenesulfonic acid sodium salt (NaDHBS), and the inorganic metal salt is CuCl2The CMOFs crystals are mof (cudhbs), otherwise as in example 1.
The aromatic sulfonate anion removal efficiency was 74.16%.
The crystal structure parameters of the mof (cudhbs) are shown in table 2.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 7
In this example, the aromatic sulfonic acid salt was 2,3,5, 6-tetrafluoro-4-hydroxybenzenesulfonic acid sodium salt (NaTFHBS), the CMOFs crystal was mof (cutfhbs), and the rest was the same as in example 1.
The aromatic sulfonate anion removal efficiency was 73.55%.
The crystal structure parameters of the mof (cutfhbs) are shown in table 2.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 8
In this example, the aromatic sulfonate is 2,4, 6-trimethylbenzenesulfonic acid sodium salt (NaTTBS), the CMOFs crystal is mof (cuttbs), and the rest is the same as in example 1.
The aromatic sulfonate anion removal efficiency was 78.63%.
The crystal structure parameters of the mof (cuttbs) are shown in table 3.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 9
In this example, the aromatic sulfonate is disodium 1, 3-benzenedisulfonate (NaBDS), the CMOFs crystals are mof (cubds), and the rest is the same as in example 1.
The aromatic sulfonate anion removal efficiency was 75.66%.
The crystal structure parameters of the mof (cubds) are shown in table 3.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 10
In this example, the aromatic sulfonate is 2-naphthalenesulfonic acid sodium salt (NaNTS), the CMOFs crystal is mof (cunts), and the rest is the same as in example 1.
The aromatic sulfonate anion removal efficiency was 78.46%.
The crystal structure parameters of the mof (cunts) are shown in table 3.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 11
In this example, the aromatic sulfonate is 6-hydroxy-2-naphthalenesulfonic acid sodium salt (NaHNTS), the CMOFs crystal is mof (cuhnts), and the rest is the same as in example 1.
The aromatic sulfonate anion removal efficiency was 74.39%.
The crystal structure parameters of the mof (cuhnts) are shown in table 3.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 3, and the stacking diagram of the CMOFs crystal is shown in FIG. 4.
Example 12
In this example, the aromatic sulfonate is 4-acetophenone benzenesulfonic acid sodium salt (NaAABS), and the inorganic metal salt is Co (NO)3)2Or Co (ClO)4)2The CMOFs crystals are mof (coaabs), otherwise as in example 1.
The aromatic sulfonate anion removal efficiency was 75.72%.
The crystal structure parameters of the mof (coaabs) are shown in table 4.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 5, and the stacking diagram of the CMOFs crystal is shown in FIG. 6.
Example 13
In this embodiment, the aromatic sulfonate is 2-aldehyde benzenesulfonic acid sodium salt (NaFBS), and the inorganic metal salt is CoCl2Or Co (BF)4)2The CMOFs crystals are mof (cofbs), otherwise as in example 1.
The aromatic sulfonate anion removal efficiency was 77.56%.
The crystal structure parameters of the mof (cofbs) are shown in table 4.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 5, and the stacking diagram of the CMOFs crystal is shown in FIG. 6.
Example 14
In this embodiment, the inorganic metal salt is FeSO4The CMOFs crystals are mof (fets), otherwise as in example 1.
The aromatic sulfonate anion removal efficiency was 75.66%.
The crystal structure parameters of the mof (fets) are shown in table 4.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 7, and the stacking diagram of the CMOFs crystal is shown in FIG. 8.
Example 15
In this example, the aromatic sulfonic acid salt was 4-nitrobenzenesulfonic acid sodium salt (NaDNBS), and the inorganic metal salt was Fe (NO)3)2Or FeCl2The CMOFs crystals are mof (fednbs), otherwise as in example 1.
The aromatic sulfonate anion removal efficiency was 77.18%.
The crystal structure parameters of the mof (fednbs) are shown in table 4.
After standing for different times, the infrared spectrum result and the powder XRD result of the CMOFs crystal show that only aromatic sulfonate anions exist in the crystal, but no inorganic anions exist, and the method has extremely strong selectivity on aromatic sulfonate anions.
The coordination environment diagram of the CMOFs crystal is shown in FIG. 7, and the stacking diagram of the CMOFs crystal is shown in FIG. 8.
TABLE 1
Figure BDA0002833377640000121
Figure BDA0002833377640000131
TABLE 2
Figure BDA0002833377640000132
TABLE 3
Figure BDA0002833377640000133
Figure BDA0002833377640000141
TABLE 4
Figure BDA0002833377640000142
Figure BDA0002833377640000151
The method successfully realizes the introduction of aromatic sulfonate anions as skeleton anions in the CMOFs by utilizing additional various intermolecular interactions such as pi-pi accumulation, hydrogen bonds, anion-pi interaction and the like among organic ligands, and fixes the aromatic sulfonate anions in CMOFs pore canals so as to realize the removal of the aromatic sulfonate anions in the aqueous solution. The method is simple to operate, mild in condition, suitable for aromatic sulfonate anions containing different groups and high in selectivity. In addition, the method successfully prepares 15 aromatic sulfonate anion CMOFs crystals while removing aromatic sulfonate anions, and CMOFs with novel structures have not been reported in related documents in previous researches. The method provides an efficient and universal synthesis method for preparing CMOFs with aromatic anions as balancing anions, and opens up a new way for the application of organic aromatic anions in MOF materials.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.

Claims (10)

1. A method for removing aromatic sulfonic acid anions in an aqueous solution is characterized by comprising the following steps: the method comprises the following steps:
adjusting the pH value of an aqueous solution containing aromatic sulfonate anions to 5-7, filtering to obtain a clarified solution, adding an ATRZ aqueous solution and an inorganic metal salt aqueous solution into the clarified solution, stirring at 20-30 ℃ for 10-30 min, filtering after stirring is finished, standing the obtained filtrate until crystals are completely separated out, and filtering to obtain a solution with the aromatic sulfonate anions removed;
wherein the molar ratio of ATRZ, aromatic sulfonate and inorganic metal salt is 3:1.5: 3-3: 2.5: 3;
the inorganic metal salt is copper salt, cobalt salt or ferrous salt;
when the inorganic metal salt is a copper salt, the aromatic sulfonate anion is TS-、ABS-、IBS-、NBS-、DNBS-、DHBS-、TFHBS-、TTBS-、BDS-、NTS-And HNTS-One or more of (1); when the inorganic metal salt is a cobalt salt, the aromatic sulfonate anion is AABS-And/or FBS-(ii) a When the inorganic metal salt is ferrous salt, the aromatic sulfonate anion is TS-And/or DNBS-。
2. The method for removing aromatic sulfonic acid anions in aqueous solution as claimed in claim 1The method is characterized in that: adjusting the pH of an aqueous solution containing aromatic sulfonate anions with an acid solution or an alkali solution, wherein the acid is HCl or H2SO4And HNO3The alkali is KOH, NaOH or Na2CO3And NaHCO3More than one of them.
3. The method for removing aromatic sulfonic acid anions from an aqueous solution according to claim 2, wherein: the alkali is NaOH and NaHCO with the mass ratio of 1:23Or the alkali is KOH and KHCO with the mass ratio of 1:23。
4. The method for removing aromatic sulfonic acid anions from an aqueous solution according to claim 1, wherein: the aqueous ATRZ solution was added first, and then the aqueous inorganic metal salt solution was added.
5. The method for removing aromatic sulfonic acid anions from an aqueous solution according to claim 1, wherein: the copper salt is Cu (NO)3)2、CuSO4、Cu(BF4)2、Cu(ClO4)2、CuBr2And CuCl2More than one of them.
6. The method for removing aromatic sulfonic acid anions from an aqueous solution according to claim 1, wherein: the cobalt salt is Co (NO)3)2、CoCl2、Co(ClO4)2And Co (BF)4)2More than one of them.
7. The method for removing aromatic sulfonic acid anions from an aqueous solution according to claim 1, wherein: the ferrous salt is FeSO4、Fe(NO3)2And FeCl2More than one of them.
8. The method for removing aromatic sulfonic acid anions from an aqueous solution according to claim 1, wherein: the standing time is 3-7 days.
9. An aromatic sulfonic acid anion CMOFs material, which is characterized in that: the material is obtained by washing and vacuum drying crystals filtered by the method of claim 1, and the CMOFs material is composed of coordination metal cations, neutral organic ligands and aromatic sulfonic acid anions, wherein the coordination metal cations are transition metal copper ions, cobalt ions or ferrous ions, and the neutral organic ligands are energetic organic ligands ATRZ with high nitrogen content;
when the metal cation is copper ion, the aromatic sulfonic acid anion is TS-、ABS-、IBS-、NBS-、DNBS-、DHBS-、TFHBS-、TTBS-、BDS-、NTS-And HNTS-One or more of (1); when the metal cation is cobalt ion, the aromatic sulfonic acid anion is AABS-And/or FBS-(ii) a When the metal cation is ferrous ion, the aromatic sulfonic acid anion is TS-And/or DNBS-。
10. The aromatic sulfonic acid anion CMOFs material of claim 9, wherein: the drying temperature is 50-80 ℃, and the drying time is 5-7 h.
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