Crown ether compound, preparation method and application thereof, and treatment method of coal chemical industry crystal carnallite

Abstract

The invention relates to the technical field of coal chemical industry crystal carnallite treatment, and discloses a crown ether compound, a preparation method and application thereof, and a coal chemical industry crystal carnallite treatment method. The structure of the crown ether compound is shown as a formula (1). The crown ether compound has an excellent anion recognition technology, and can effectively recognize and complex anions OH <->, SiO3 < 2->, SO4 < 2-> and PO4 < 3->, so that harmless treatment of the coal chemical industry crystal carnallite can be effectively realized, and the pollution of the coal chemical industry crystal carnallite to the environment is reduced. Formula (1)

Description

Technical Field

[0001] This invention relates to the field of coal chemical crystallization salt treatment technology, specifically to a crown ether compound, its preparation method, and its application in the treatment of coal chemical crystallization salts. Background Technology

[0002] Coal chemical crystalline salts are obtained through the evaporation and crystallization of high-salt wastewater from coal chemical plants. They possess high-risk characteristics, including high concentrations of inorganic salt ions, complex organic pollutants, and high levels of heavy metals. The crystalline salts obtained after evaporation and crystallization of concentrated coal chemical wastewater mainly exist in the forms of sodium salts (such as sodium sulfate and sodium phosphate), potassium salts (such as potassium sulfate and potassium phosphate), magnesium salts (such as magnesium sulfate and magnesium phosphate), calcium salts (such as calcium sulfate and calcium phosphate), and alkali salts (such as sodium hydroxide). Currently, the traditional treatment method for coal chemical crystalline salts is to pre-treat them before landfilling them according to hazardous waste treatment requirements. For example, a coal chemical company uses rigid landfill technology to treat crystalline salts: first, high-strength, low-permeability concrete is used to construct the landfill space, and then high-density polyethylene (HPDE) material is used for seepage prevention, ultimately achieving rigid landfilling of the crystalline salts. However, rigid landfill technology has significant drawbacks: harmful substances in the crystalline salts (such as sulfates, phosphates, and alkali salts) cannot be effectively solidified, and long-term exposure to the natural environment makes them susceptible to leaching by rainwater, leading to SO42---. 2- PO4 2- OH - Anions migrate to the surrounding soil and water bodies, causing problems such as surface water pollution, groundwater salinization, and soil salinization, posing a serious threat to the ecological environment.

[0003] Therefore, developing a new strategy for treating coal chemical crystallized salts to reduce the impact of harmful substances on the ecological environment is an urgent technical problem to be solved. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of existing technologies that cannot effectively treat crystalline impurities in coal chemical processes. This invention provides a crown ether compound, its preparation method, and its application in treating crystalline impurities in coal chemical processes. This crown ether compound possesses excellent anion recognition technology and can effectively treat OH- anions. - SiO3 2- SO4 2- and PO4 3- By effectively identifying and complexing these salts, the harmless treatment of coal chemical crystalline salts can be achieved, reducing the environmental pollution caused by these salts.

[0005] To achieve the above objectives, the present invention provides a crown ether compound, the structure of which is shown in formula (1);

[0006] Equation (1).

[0007] A second aspect of the present invention provides a method for preparing the above-mentioned crown ether compounds, the method comprising: reacting 4'-aminobenzo-15-crown-5-ether with diphenylmethane diisocyanate; The weight ratio of 4'-aminobenzo-15-crown-5-ether to diphenylmethane diisocyanate is 1:(0.4-0.5).

[0008] Preferably, the specific process of the method includes: mixing the 4'-aminobenzo-15-crown-5-ether with organic solvent A to obtain a solution containing 4'-aminobenzo-15-crown-5-ether; mixing the diphenylmethane diisocyanate with organic solution B to obtain a solution containing diphenylmethane diisocyanate; and then mixing the solution containing 4'-aminobenzo-15-crown-5-ether and the solution containing diphenylmethane diisocyanate for reaction.

[0009] Preferably, the organic solvent A is acetonitrile.

[0010] Preferably, the organic solvent B is acetonitrile.

[0011] Preferably, the reaction conditions include a temperature of 75-80°C and a time of 1-3 hours.

[0012] Preferably, the method further includes: separating the reacted material into solid and liquid phases, and purifying the solid product.

[0013] Preferably, the purification process includes: performing column chromatography on the solid-phase product, using a mixture of petroleum ether and ethyl acetate with a volume ratio of 2-5:1 as the eluent, and then concentrating the eluted solution under reduced pressure to obtain the crown ether compound.

[0014] The third aspect of this invention provides the application of the above-mentioned crown ether compounds as anion recognition agents in the anion recognition process.

[0015] Preferably, the anion is selected from OH. - SiO3 2- SO4 2- and PO4 3- One or more of them.

[0016] The fourth aspect of this invention provides the application of the above-mentioned crown ether compounds as complexing agents in the process of complexing anions in coal chemical crystalline miscellaneous salts.

[0017] Preferably, the anion in the coal chemical crystalline miscellaneous salt is selected from OH. -SiO3 2- SO4 2- and PO4 3- One or more of them.

[0018] The fifth aspect of the present invention provides a method for treating coal chemical crystalline impurities, the method comprising: mixing the crown ether compound with a solution containing coal chemical crystalline impurities to carry out a complexation reaction; The anions contained in the coal chemical crystalline miscellaneous salts are selected from OH-. - SiO3 2- SO4 2- and PO4 3- One or more of them.

[0019] Preferably, the molar ratio of the crown ether compound to the anion in the coal chemical crystalline miscellaneous salt is 1:0.5-2.5.

[0020] The crown ether compounds of this invention have the structure shown in formula (1), wherein the crown ether compounds contain a crown ether ring and a urea group (bifunctional group), and the crown ether compounds have anion recognition and anion complexing capabilities. Specifically, the crown ether compounds can recognize OH-. - SiO3 2- SO4 2- PO4 3- Crown ethers, being anions, can be widely used as anion recognition agents, and can also act as complexing agents with OH groups. - SiO3 2- SO4 2- PO4 3- The anionic complexes formed by the induction of crown ether compounds and anions immobilize the anions in the coal chemical crystalline salts, thereby further preventing the presence of OH groups in the coal chemical crystalline salts. - SiO3 2- SO4 2- PO4 3- The migration of anions to surrounding soil or water bodies reduces the impact on the ecological environment and has broad application prospects in the harmless treatment of crystalline miscellaneous salts in coal chemical industry. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the process for preparing crown ether compounds in Example 1 of the present invention; Figure 2 This is the 1H NMR spectrum of the crown ether compounds described in this invention; Figure 3 This is the infrared spectrum of the crown ether compounds described in this invention; Figure 4The solution containing crown ether compounds described in this invention and different Na content + The result of UV-Vis spectroscopy after the solution containing anions was mixed thoroughly. Figure 5 The solution containing crown ether compounds described in this invention and different TBA contents + The result of UV-Vis spectroscopy after the solution containing anions was mixed thoroughly. Figure 6 This is a UV-Vis test result image of a solution containing crown ether compounds as described in this invention after being mixed evenly with a solution containing NaOH. Figure 7 This is a graph showing the UV-Vis test results after the solution containing crown ether compounds described in this invention is mixed evenly with a solution containing (TBA)2SO4. Figure 8 The crown-containing ether compounds and anions (OH-) described in this invention - Combined with the results of the ultraviolet titration experiment; Figure 9 The crown-containing ether compound and anion (SO4) described in this invention 2- (See the diagram showing the results of the UV titration experiment.) Detailed Implementation

[0022] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0023] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] The structure of the crown ether compounds described in this invention is shown in formula (1);

[0025] Equation (1).

[0026] In this invention, the crown ether compound contains both a crown ether ring and a urea group, making it bifunctional. This crown ether compound possesses anion recognition functionality and can be used as an anion recognizer. Specifically, the crown ether compound can recognize OH-. - SiO3 2- SO4 2- and PO4 3-The crown ether compound can effectively identify one or more of the anions and can be used as an anion recognizer. Furthermore, after recognizing these anions, the crown ether compound can further act as a complexing agent to complex with the anions, thereby forming a complex containing the crown ether compound and the anion, thus enabling the removal of OH- ions from the solution. - SiO3 2- SO4 2- and PO4 3- The efficient complexation of anions further prevents their migration into surrounding soil and water bodies, thus avoiding environmental pollution. Therefore, the crown ether compound described in this invention can be used as a complexing agent to effectively pretreat anions in coal chemical crystalline salts, thereby significantly reducing the environmental harm caused by coal chemical crystalline salts.

[0027] The present invention further provides a method for preparing the crown ether compound described above, the method comprising: reacting 4'-aminobenzo-15-crown-5-ether with diphenylmethane diisocyanate.

[0028] In the method described in this invention, the 4'-aminobenzo-15-crown-5-ether and the diphenylmethane diisocyanate are reacted as reactants to obtain a crown ether compound with the structure shown in formula (1).

[0029] In the method described in this invention, the weight ratio of the 4'-aminobenzo-15-crown-5-ether to the diphenylmethane diisocyanate is 1:(0.4-0.5), preferably 1:(0.42-0.48). Specifically, the weight ratio of the 4'-aminobenzo-15-crown-5-ether to the diphenylmethane diisocyanate can be 1:0.4, 1:0.41, 1:0.42, 1:0.43, 1:0.44, 1:0.45, 1:0.46, 1:0.47, 1:0.48, 1:0.49, or 1:0.5.

[0030] In some embodiments, the specific process of the method of the present invention includes: mixing the 4'-aminobenzo-15-crown-5-ether with the organic solvent A to obtain a solution containing 4'-aminobenzo-15-crown-5-ether; mixing the diphenylmethane diisocyanate with the organic solvent B to obtain a solution containing diphenylmethane diisocyanate; and then mixing the solution containing 4'-aminobenzo-15-crown-5-ether and the solution containing diphenylmethane diisocyanate to react and obtain a crown ether compound with the structure shown in formula (1).

[0031] In this invention, the type of organic solvent A is not particularly limited and can be any aprotic solvent commonly used in the art. In some embodiments, organic solvent A can be acetonitrile.

[0032] In some embodiments, the weight ratio of 4'-aminobenzo-15-crown-5-ether to the organic solvent A is 1:15-16.

[0033] In this invention, the type of organic solvent B is not particularly limited and can be any aprotic solvent commonly used in the art. In some embodiments, the organic solvent B can be acetonitrile.

[0034] In some embodiments, the weight ratio of diphenylmethane diisocyanate and organic solvent B is 1:60-75.

[0035] In some preferred embodiments, the reaction conditions include a temperature of 75-80°C and a time of 1-3 hours. By limiting the reaction conditions to the above range, higher purity of the prepared crown ether compounds can be ensured. Specifically, the reaction temperature can be 75°C, 76°C, 77°C, 78°C, 79°C, or 80°C; the reaction time can be 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours, or 3 hours.

[0036] In some embodiments, the method further includes: separating the reacted materials into solid and liquid phases, and purifying the solid-phase product. Specifically, the solid-phase product is the crude product of the crown ether compound.

[0037] In some embodiments, the solid product may be washed and dried with a solvent before purification, and then the dried solid product may be purified.

[0038] In a preferred embodiment, the purification is performed using column chromatography to purify the solid-phase product. Specifically, the purification process includes: subjecting the solid-phase product to column chromatography, using a mixture of petroleum ether and ethyl acetate at a volume ratio of 2-5:1 as the eluent, then collecting the eluted solution and concentrating it under reduced pressure to obtain the purified crown ether compound.

[0039] In some preferred embodiments, the volume ratio of petroleum ether to ethyl acetate in the eluent is 2.5-4:1. Specifically, the volume ratio of petroleum ether to ethyl acetate in the eluent can be 2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, or 5:1.

[0040] The crown ether compounds described in this invention possess anion recognition capabilities and can be used as anion recognition agents to identify anions. Specifically, the anion is selected from OH-. -SiO3 2- SO4 2- and PO4 3- One or more of the following. Furthermore, and more importantly, the crown ether compounds of this invention, after recognizing anions, can also act as complexing agents to complex the anions, thereby forming a complex containing the crown ether compound and the anion, preventing the anions from migrating to surrounding areas and causing environmental pollution. Therefore, the crown ether compounds of this invention can be used as complexing agents to treat anions (OH-) contained in coal chemical crystalline miscellaneous salts. - SiO3 2- SO4 2- and PO4 3- It can efficiently complex one or more of the following substances to achieve harmless treatment of coal chemical crystalline salts and reduce the pollution of coal chemical crystalline salts to the environment.

[0041] In this invention, the crown ether compounds can be used as complexing agents to pretreat coal chemical crystalline salts before subsequent landfill disposal. The crown ether compounds complex the anions in the coal chemical crystalline salts, preventing the anions from diffusing and causing pollution. Specifically, the specific operational method for pretreating the coal chemical crystalline salts is not particularly limited.

[0042] In some embodiments, the present invention further provides a pretreatment method for coal chemical crystalline heterosalts, the method comprising: mixing the crown ether compound with a solution containing the coal chemical crystalline heterosalt to perform a complexation reaction. Specifically, the anion contained in the coal chemical crystalline heterosalt is selected from OH. - SiO3 2- SO4 2- and PO4 3- One or more of the following. The crown ether compound undergoes a complexation reaction with the anions in the coal chemical crystalline salt to obtain a complex containing the crown ether compound and the anions. This can fix the anions in the macromolecular complex, further preventing the anions in the coal chemical crystalline salt from migrating to the surrounding soil and water bodies, reducing the pollution of the coal chemical crystalline salt to the environment, and thus achieving the harmless treatment of the coal chemical crystalline salt.

[0043] In some preferred embodiments, in order to further improve the complexation rate of the crown ether compound for anions in coal chemical crystalline miscellaneous salts, the molar ratio of the crown ether compound to the anions in the coal chemical crystalline miscellaneous salts is 1:0.5-2.5, preferably 1:0.8-1.8, and more preferably 1:0.9-1.5.

[0044] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto. A schematic diagram of the preparation process in Example 1 is shown below. Figure 1 As shown.

[0045] Example 1 S1. Mix 0.1 g of 4'-aminobenzo-15-crown-5-ether with 2 mL of acetonitrile (CH3CN) and stir to form a colorless and transparent solution A1; S2. Mix 0.0442g of diphenylmethane diisocyanate with 4mL of acetonitrile (CH3CN) and stir continuously until the solution is clear to obtain a pale yellow clear solution B1. S3. Place the colorless and transparent solution A1 in a flask, then add the pale yellow and clear solution B1, add a magnetic stir bar, and stir the reaction at 80°C. Monitor the reaction by thin-layer chromatography. After 2 hours of reaction, obtain the reaction mixture. Filter the reaction mixture, collect the solid product, wash the solid product with acetone, and dry it to obtain the crude product of crown ether compounds. S4. Using a mixture of petroleum ether and ethyl acetate (volume ratio of petroleum ether to ethyl acetate is 3:1) as the eluent, the crude product of the crown ether compound is purified by column chromatography. The eluted solution is collected and concentrated under reduced pressure to obtain the purified crown ether compound.

[0046] Example 2 S1. Mix 0.1 g of 4'-aminobenzo-15-crown-5-ether with 2 mL of acetonitrile (CH3CN) and stir to form a colorless and transparent solution A1; S2. Mix 0.0489 g of diphenylmethane diisocyanate with 4 mL of acetonitrile (CH3CN) and stir continuously until the solution is clear to obtain a pale yellow clear solution B2. S3. Place the colorless and transparent solution A1 in a flask, then add the pale yellow and clear solution B2, add a magnetic stir bar, and stir the reaction at 75°C. Monitor the reaction by thin-layer chromatography. After 3 hours of reaction, obtain the reaction mixture. Filter the reaction mixture, collect the solid product, wash the solid product with acetone, and dry it to obtain the crude product of crown ether compounds. S4. Using a mixture of petroleum ether and ethyl acetate (volume ratio of petroleum ether to ethyl acetate is 3:1) as the eluent, the crude product of the crown ether compound is purified by column chromatography. The eluted solution is collected and concentrated under reduced pressure to obtain the purified crown ether compound.

[0047] Test case Test Example 1 The crown ether compounds prepared in Example 1 of this invention were subjected to 1H NMR and IR spectroscopy, and the results are as follows: Figure 2 and Figure 3 As shown. Figure 2 The above is the 1H NMR spectrum of the crown ether compound in Example 1 of this invention; Figure 3 The image shows the infrared spectrum of the crown ether compound in Example 1 of this invention.

[0048] Depend on Figure 2 It can be seen that the characteristic peaks at 8.51 ppm and 8.45 ppm belong to the four hydrogens on the urea group; the characteristic peaks with chemical shifts between 6.87 and 7.39 ppm belong to the 14 hydrogens on the four benzene rings; the characteristic peak at chemical shift 3.83 ppm is the characteristic peak of the two hydrogens at the alkyl group connecting the intersection of the symmetrical structure; and the characteristic peaks with chemical shifts at 4.03 ppm, 3.78 ppm, and 3.63 ppm belong to the 32 hydrogens on the crown ether ring. Figure 3 It can be seen that there is an NH bond stretching vibration peak and a peak at 2943 cm⁻¹. -1 1595 cm -1 The C=O bond stretching vibration peak. 1595 cm⁻¹ -1 The peak at 1510 cm⁻¹ is the stretching vibration peak of the C=O bond in the urea group. -1 The peak at 3278 cm⁻¹ corresponds to the bending vibration mode of the NH bond in the urea group. -1 The peak at 1227 cm⁻¹ is the stretching vibration peak of the NH bond in the urea group. These characteristic peaks together constitute the diagnostic peaks of the urea group; -1 A symmetric stretching vibration peak of the urea group CN group was detected at 1348 cm⁻¹. -1 The peak at 2943 cm⁻¹ represents the bond vibration peak of the aromatic ring conjugated system. -1 The peak at 1134 cm⁻¹ corresponds to the vibration of the methylene group in the diphenylmethane structure. -1 The peak at that point is attributed to the stretching vibration of the COC bond in the crown ether ring. The above results indicate that the present invention has prepared crown ether compounds with the structure shown in formula (1).

[0049] Test Example 2 The anion recognition ability and anion complexing ability of the crown ether compounds prepared in Example 1 of this invention were tested.

[0050] (1) Anion recognition selective recognition experiment Preparation of a solution containing crown ether compounds: Dimethyl sulfoxide (DMSO) and acetonitrile (CH3CN) were mixed thoroughly at a volume ratio of 1:99 to obtain a mixed solvent. The crown ether compounds were then added to the mixed solvent to achieve a final concentration of 2 × 10⁻⁶. -5 A solution containing crown ether compounds was prepared by using mol / L.

[0051] Sodium chloride (NaCl), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), tetrabutylammonium chloride (TBACl), tetrabutylammonium hydroxide (TBAOH), tetrabutylammonium fluoride (TBAF), tetrabutylammonium sulfate ((TBA)2SO4), and tetrabutylammonium phosphate ((TBA)3PO4) were used as test samples. The test samples were mixed thoroughly with a mixed solvent (dimethyl sulfoxide and acetonitrile mixed at a volume ratio of 1:99) to prepare solutions containing NaCl, NaOH, Na2SiO3, TBACl, TBAOH, TBAF, (TBA)2SO4, and (TBA)3PO4, respectively. The final concentration of the test sample in the sample-containing solutions was 4 × 10⁻⁶. -3 mol / L; Sodium sulfate (Na₂SO₄) and sodium phosphate (Na₃PO₄) were used as samples, and the samples were added to aqueous solutions to achieve a final concentration of 4 × 10⁻⁶. -3 Solutions containing Na2SO4 and Na3PO4 were prepared using mol / L.

[0052] Solutions containing NaCl, NaOH, Na₂SiO₃, Na₂SO₄, and Na₃PO₄ were respectively considered as solutions containing Na₂SiO₃. + A solution containing anions, 3 mL of a solution containing crown ether compounds and 30 μL of a solution containing Na+ + After thoroughly mixing with the anion solution, UV-Vis spectroscopy was performed, and the results are as follows. Figure 4 As shown. Among them, in Figure 4 In the text, crown ether compounds represent the results of UV-Vis spectroscopy measurements of solutions containing crown ether compounds; SiO3 2- The results of UV-Vis spectroscopy analysis were performed after a solution containing crown ether compounds was thoroughly mixed with a solution containing Na₂SiO₃; PO₄ 3- The results of UV-Vis spectroscopy analysis were performed after a solution containing crown ether compounds was thoroughly mixed with a solution containing Na3PO4; Cl - The results of UV-Vis spectroscopy analysis were performed after a solution representing a crown ether compound was thoroughly mixed with a solution containing NaCl; OH - The results of UV-Vis spectroscopy analysis were performed after a solution containing crown ether compounds was thoroughly mixed with a solution containing NaOH; SO4 2- The results of UV-Vis spectroscopy analysis were obtained after a solution containing crown ether compounds was thoroughly mixed with a solution containing Na2SO4. Solutions containing TBACl, TBAOH, TBAF, (TBA)₂SO₄, and (TBA)₃PO₄ were respectively considered as solutions containing TBA. + Solutions containing anions; mix 3 mL of a solution containing crown ether compounds with 30 μL of a solution containing TBA. + After thoroughly mixing with the anion solution, UV-Vis spectroscopy was performed, and the results are as follows. Figure 5 As shown. Among them, in Figure 5 In the text, crown ether compounds represent the results of UV-Vis spectroscopy measurements of solutions containing crown ether compounds. OH - The results of UV-Vis spectroscopy analysis were performed after a solution containing crown ether compounds was thoroughly mixed with a solution containing TBAOH. (SO4) 2- The results of UV-Vis spectroscopy analysis were performed after a solution containing crown ether compounds was thoroughly mixed with a solution containing (TBA)₂SO₄. (PO₄) 3- The result of UV-Vis spectroscopy analysis after uniformly mixing a solution containing crown ether compounds with a solution containing (TBA)3PO4, F - The results of UV-Vis spectroscopy analysis were performed after a solution containing crown ether compounds was thoroughly mixed with a solution containing TBAF. (Cl) - The results of UV-Vis spectroscopy analysis were obtained after a solution containing crown ether compounds was thoroughly mixed with a solution containing TBACl.

[0053] Depend on Figure 4 and Figure 5 It can be seen that the absorption peak of the solution containing crown ether compounds is located at 265 nm. From... Figure 4 It can be seen that in the presence of Na + In solutions containing anions, the characteristic peak at 265 nm shifted when different anions came into contact with crown ether compounds: OH - The spectral shift caused by SiO3 is the largest, with a 2 nm redshift; 2- There is a 1 nm redshift; the dynamic change in absorption peak reflects the effect of the crown ether compound in Example 1 of this invention on the anion (OH-). - SiO3 2- The recognition mechanism of ) can form specific complexes, especially with OH - The complexation is most prominent.

[0054] Depend on Figure 5 It can be seen that, in the case of TBA + In solutions containing anions, the characteristic peak at 265 nm shifted when different anions came into contact with crown ether compounds: SO4 2- The most significant spectral shift was observed, with a 4 nm redshift, in PO4. 3- and OH -Both can induce a 2 nm redshift; the absorption peak shift energy shows that the crown ether compounds in Example 1 of this invention have the ability to recognize SO4. 2- PO4 3- and OH - The ability to complex with these anions to form complexes containing crown ether compounds and anions, including those with SO4. 2- The complexation is most obvious.

[0055] (2) Anion binding ratio determination experiment To investigate the complexation properties of crown ether compounds with anions, OH- - and SO4 2- An anion binding ratio was determined using these two anions as examples.

[0056] Preparation of a solution containing crown ether compounds: Dimethyl sulfoxide (DMSO) and acetonitrile (CH3CN) were mixed thoroughly at a volume ratio of 1:99 to obtain a mixed solvent; the crown ether compounds were then added to the mixed solvent to achieve a final concentration of 2 × 10⁻⁶. -5 A solution containing crown ether compounds was prepared by using mol / L.

[0057] Prepare the test solutions, which are solutions containing NaOH and (TBA)₂SO₄. The specific preparation methods are as follows: Preparation of a NaOH solution: Mix dimethyl sulfoxide (DMSO) and acetonitrile (CH3CN) at a volume ratio of 1:99 to obtain a mixed solvent; add NaOH to the mixed solvent to make the final NaOH concentration 2×10⁻⁶. -5 A solution containing NaOH was prepared by using mol / L.

[0058] Preparation of a solution containing (TBA)₂SO₄: Mix dimethyl sulfoxide (DMSO) and acetonitrile (CH₃CN) at a volume ratio of 1:99 to obtain a mixed solvent; add (TBA)₂SO₄ to the mixed solvent to make the final concentration of (TBA)₂SO₄ 2 × 10⁻⁶. -5 A solution containing (TBA)₂SO₄ was prepared by using mol / L.

[0059] Following a molar ratio of crown ether compound to anion (1-10 : (9-0), the solution containing the crown ether compound was thoroughly mixed with the test solution to obtain a complex solution containing the crown ether compound and anion. Absorption spectral data of both the solution containing the crown ether compound and the complex solution containing the crown ether compound and anion were collected using a UV-Vis spectrometer. The concentration of the complex solution containing the crown ether compound and anion (referred to as the complex concentration) was calculated using the absorbance values ​​of specific absorption peaks according to the following formula:

[0060] Where A0 represents the absorbance of the solution containing crown ether compounds, A represents the absorbance of the mixture of crown ether compounds and anionic complexes, [H] is the concentration of crown ether compounds, and [HG] is the concentration of complexes.

[0061] A UV Job's plot was used to determine the molar fraction of [HG] and the anion to establish the complexation ratio between the host (crown ether compound) and the guest (anion). The results are as follows: Figure 6 and Figure 7 As shown, the corresponding results are recorded in Table 1. Figure 6 The results are obtained after thoroughly mixing a solution containing crown ether compounds with a solution containing NaOH. Figure 6 (a) represents crown ether compounds and OH in different molar ratios. - The UV spectrum of the mixture containing crown ether compounds and anions after complexation. Figure 6 (b) represents crown ether compounds and OH in different molar ratios. - After complexation, at 265 nm, the concentration of the complex containing the crown ether compound and the anion is related to the OH group. - The UV Job's plot; Figure 7 The results are obtained after a solution containing crown ether compounds is thoroughly mixed with a solution containing (TBA)₂SO₄. Figure 7 (a) represents crown ether compounds and SO4 in different molar ratios. 2- The UV spectrum of the mixture containing crown ether compounds and anions after complexation. Figure 7 (b) represents crown ether compounds and SO4 in different molar ratios. 2- After complexation, at 265 nm, the concentration of the complex containing the crown ether compound and the anion is related to SO42-. 2- The UV Job's plot. Among them, Figure 6 (a) and Figure 7In (a), 10[H] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 1:0; 9[H]+1[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.9:0.1; 8[H]+2[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.8:0.2; 7[H]+3[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.7:0.3; 6[H]+4[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.6:0.4; 5 [H]+5[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.5:0.5; 4[H]+6[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.4:0.6; 3[H]+7[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.3:0.7; 2[H]+8[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.2:0.8; and 1[H]+9[G] represents the UV spectrum obtained when the molar ratio of crown ether compound [H] to anion [G] is 0.1:0.9.

[0062] Table 1. Molar ratio of crown ether compounds to anions, mole fraction of anions, absorbance of the complexes of crown ether compounds and anions at 265 nm, and concentration of the complexes of crown ether compounds and anions.

[0063] Note: The absorbance of the complex in the NaOH system represents the reaction between crown ether compounds and OH. - The absorbance of the mixture of complexes; in the NaOH system, [HG] represents the crown ether compound and OH. - The concentration of the complex; the absorbance of the complex in the (TBA)₂SO₄ system represents the concentration of the crown ether compound and SO₄. 2- The absorbance of the mixture of complexes; in the (TBA)₂SO₄ system, [HG] represents the crown ether compound and SO₄. 2- The concentration of the complex.

[0064] Depend on Figure 6 and Figure 7Combined with the data in Table 1, it can be seen that when the molar ratio of crown ether compounds to anions is 0.5:0.5, the concentration of the complex reaches its maximum, confirming the interaction between crown ether compounds and OH-. - or SO4 2- Identified by a 1:1 binding mode, crown ether compounds can bind with OH groups. - and SO4 2- Anionic complexes are formed by the combination of anions and crown ether compounds.

[0065] (3) Anion binding ultraviolet titration experiment To further investigate the formation of complexes containing crown ether compounds and anions by complexing with crown ether compounds and anions, OH- - and SO4 2- An anion binding ultraviolet titration experiment was conducted using these two anions as examples.

[0066] Preparation of solutions containing crown ether compounds: Dimethyl sulfoxide (DMSO) and acetonitrile (CH3CN) were mixed thoroughly at a volume ratio of 1:99 to obtain a mixed solvent; the crown ether compound was added to the mixed solvent to make the final concentration of the crown ether urea complexing agent 2 × 10⁻⁶. -5 A solution containing crown ether compounds was prepared by using mol / L.

[0067] Preparation of a NaOH solution: Mix dimethyl sulfoxide (DMSO) and acetonitrile (CH3CN) at a volume ratio of 1:99 to obtain a mixed solvent; add NaOH to the mixed solvent to achieve a final NaOH concentration of 2×10⁻⁶. -3 mol / L, 4×10 -3 mol / L, 2×10 -2 Solutions containing NaOH of different concentrations were prepared by using mol / L.

[0068] Preparation of a solution containing (TBA)₂SO₄: Dimethyl sulfoxide (DMSO) and acetonitrile (CH₃CN) were mixed thoroughly at a volume ratio of 1:99 to obtain a mixed solvent; (TBA)₂SO₄ was added to the mixed solvent to achieve a final concentration of 2 × 10⁻⁶. - 3 mol / L, 4×10 -3 mol / L, 2×10 -2 Solutions containing (TBA)₂SO₄ of different concentrations were prepared by using mol / L.

[0069] 3 mL of a concentration of 2×10 -5 A solution of crown ether compounds at a concentration of mol / L was used as a standard, and 3 μL of 2 × 10⁻⁶ mol / L solution was added dropwise in successive additions. -3Six times, 3 μL of mol / L (0.1 equivalent) NaOH solution containing NaOH, 4 × 10⁻⁶ -3 4 times, 3 μL of mol / L (0.2 equivalent) NaOH solution containing NaOH, 2×10 -2 A solution containing mol / L (1 equivalent) of NaOH was added twice. After each addition, the solution was stirred thoroughly, and the UV-Vis spectra were measured and recorded immediately. A complete titration curve was prepared, and finally, the titration results of crown ether compounds and OH groups were plotted. - Combined ultraviolet-visible absorption spectra, such as Figure 8 As shown; Figure 8 The present invention is an anion (OH-). - Combined with ultraviolet titration experiments, among which Figure 8 (a) is a crown ether compound with OH - The ultraviolet titration curve; Figure 8 (b) is OH - The relationship between equivalent and absorbance. Among them, in Figure 8 In (a), L represents the absorbance of the solution containing crown ether compounds, L + 0.1OH - The absorbance of the mixture after the first addition of (0.1 equivalents) of a NaOH-containing solution, L+0.2OH - The absorbance of the mixture after the second addition of (0.1 equivalent) NaOH solution is given, L+0.3OH. - The absorbance of the mixture after the third addition (0.1 equivalents) of a NaOH-containing solution, L+0.4OH - The absorbance of the mixture after the fourth addition of (0.1 equivalent) NaOH solution is given, L+0.5OH. - The absorbance of the mixture after the 5th addition (0.1 equivalents) of a NaOH-containing solution, L+0.6OH - The absorbance of the mixture after the 6th addition (0.1 equivalents) of a NaOH-containing solution, L+0.8OH - The absorbance of the mixture after the 7th addition (0.2 equivalents) of a NaOH-containing solution, L+1.0OH - The absorbance of the mixture after the 8th addition of a solution containing NaOH (0.2 equivalents), L+1.2OH - The absorbance of the mixture after the 9th addition (0.2 equivalents) of a NaOH-containing solution, L+1.4OH - The absorbance of the mixture after the 10th addition (0.2 equivalents) of a NaOH-containing solution, L+2.4OH - The absorbance of the mixture after the 11th addition (1 equivalent) of a NaOH-containing solution, L+3.4OH -This represents the absorbance of the mixed system after the 12th addition (1 equivalent) of a NaOH-containing solution.

[0070] 3 mL of a concentration of 2×10 -5 A solution of crown ether compounds at a concentration of mol / L was used as a standard, and 3 μL of 2 × 10⁻⁶ mol / L solution was added dropwise in successive additions. -3 Six mol / L (0.1 equivalent) solutions containing (TBA)₂SO₄, 3 μL each, 4 × 10⁻⁶ -3 Five 3 μL solutions containing (TBA)₂SO₄ at a concentration of mol / L (0.2 equivalent) were administered. -2 A solution containing (TBA)₂SO₄ in mol / L (1 equivalent) solution was added three times. After each addition, the solution was stirred thoroughly, and the UV-Vis spectra were measured and recorded immediately. A complete titration curve was prepared, and finally, the titration results of crown ether compounds and SO₄²⁻ were plotted. 2- Combined ultraviolet-visible absorption spectra, such as Figure 9 As shown; Figure 9 The present invention is an anion (SO4) 2- Combined with ultraviolet titration experiments, among which Figure 9 (a) is a crown ether compound with SO4 2- The ultraviolet titration curve; Figure 9 (b) is SO4 2- The relationship between equivalent and absorbance. Among them, in Figure 9 In (a), L represents the absorbance of the solution containing crown ether compounds, L + 0.1SO4 2- The absorbance of the mixture after the first addition of (0.1 equivalents) of a solution containing (TBA)₂SO₄, L + 0.2SO₄ 2- The absorbance of the mixture after the second addition of (0.1 equivalents) of a solution containing (TBA)₂SO₄, L + 0.3SO₄ 2- The absorbance of the mixture after the third addition of (0.1 equivalents) of a solution containing (TBA)₂SO₄, L + 0.4SO₄ 2- The absorbance of the mixture after the fourth addition of (0.1 equivalents) of a solution containing (TBA)₂SO₄, L + 0.5SO₄ 2- The absorbance of the mixture after the 5th addition of (0.1 equivalents) of a solution containing (TBA)₂SO₄, L + 0.6SO₄ 2- The absorbance of the mixture after the 6th addition of (0.1 equivalents) of a solution containing (TBA)₂SO₄, L + 0.8SO₄ 2- The absorbance of the mixture after the 7th addition of (0.2 equivalents) of a solution containing (TBA)₂SO₄, in L + 1.0SO₄. 2-The absorbance of the mixture after the 8th addition of (0.2 equivalents) of a solution containing (TBA)₂SO₄, L + 1.2SO₄ 2- The absorbance of the mixture after the 9th addition of (0.2 equivalents) of a solution containing (TBA)₂SO₄, L + 1.4SO₄ 2- The absorbance of the mixture after the 10th addition of (0.2 equivalents) of a solution containing (TBA)₂SO₄, L + 1.6SO₄ 2- The absorbance of the mixture after the 11th addition of (0.2 equivalents) of a solution containing (TBA)₂SO₄, L + 2.6SO₄ 2- The absorbance of the mixture after the 12th addition (1 equivalent) of a solution containing (TBA)₂SO₄, L + 3.6SO₄ 2- The absorbance of the mixture after the 13th addition (1 equivalent) of a solution containing (TBA)₂SO₄, L + 4.6SO₄ 2- The absorbance represents the absorbance of the mixed system after the 14th addition of a solution containing (TBA)₂SO₄ (1 equivalent).

[0071] The nonlinear fitting method is used to obtain the binding constant (K) according to the following formula. a ):

[0072] In the formula, A and A limit The absorbance and maximum value of the mixed system after adding different concentrations of anions are shown at the selected wavelength (285 nm); A0 is the absorbance of the crown ether compound at the selected wavelength (285 nm); C0 is the initial concentration of the crown ether compound; K a is the binding constant of the complex; x is the molar concentration of anions in the mixture after each addition of anions.

[0073] Depend on Figure 8 As can be seen from (a), with the anion (OH-) - With the continuous addition of [unspecified compound], the absorption curve in the visible light region continued to fluctuate. Spectroscopic analysis showed an isoabsorption point at 268 nm, indicating that crown ether compounds react with hydroxide ions (OH-). - A stable complex was formed, and the change in the UV titration curve confirmed the interaction between the host (crown ether compound) and the guest (OH group). - The combination of OH groups. This was achieved through analysis of OH groups. - The absorbance curve of the system at 285 nm wavelength was obtained by nonlinear fitting method to determine the relationship between crown ether compounds and OH groups. - The binding constant ( K a The value is 10625.64 M. -1 ( Figure 8 (b)

[0074] Depend on Figure 9 As can be seen from (a), with the anion (SO4) 2- With the continuous addition of ), the absorption curve in the visible light region fluctuates continuously, and spectral analysis shows a clear isoabsorption point at 267 nm. This indicates that crown ether compounds react with sulfate ions (SO42-) 2- A stable complex was formed, and the change in the UV titration curve confirmed that the host (crown ether compound) and the guest (SO4) were related. 2- The combination of SO4. Through analysis of SO4 2- The absorbance curve of the system at a wavelength of 285 nm was obtained by nonlinear fitting method to determine the relationship between crown ether compounds and SO4. 2- The binding constant ( K a The value is 38753.38 M. -1 ( Figure 9 (b)

[0075] The test examples confirm that the crown ether compounds described in this invention possess anion recognition capabilities and can also react with OH groups. - SiO3 2- SO4 2- PO4 3- The anions are complexed to form a complex, which can prevent the anions in coal chemical crystallized salts from spreading to the surrounding soil or water and causing environmental pollution, thus achieving the harmless treatment of coal chemical crystallized salts.

[0076] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A crown ether compound, characterized in that, The structure of the crown ether compounds is shown in formula (1); Equation (1).

2. A method for preparing the crown ether compound according to claim 1, characterized in that, The method includes reacting 4'-aminobenzo-15-crown-5-ether with diphenylmethane diisocyanate.

3. The method according to claim 2, characterized in that, The specific process of the method includes: mixing the 4'-aminobenzo-15-crown-5-ether with organic solvent A to obtain a solution containing 4'-aminobenzo-15-crown-5-ether; mixing the diphenylmethane diisocyanate with organic solution B to obtain a solution containing diphenylmethane diisocyanate; and then mixing the solution containing 4'-aminobenzo-15-crown-5-ether and the solution containing diphenylmethane diisocyanate for reaction.

4. The method according to claim 3, characterized in that, The organic solvent A is acetonitrile; and / or The organic solvent B is acetonitrile.

5. The method according to any one of claims 2-4, characterized in that, The reaction conditions include a temperature of 75-80℃ and a time of 1-3 hours.

6. The method according to any one of claims 2-5, characterized in that, The weight ratio of 4'-aminobenzo-15-crown-5-ether to diphenylmethane diisocyanate is 1:(0.4-0.5).

7. The method according to any one of claims 2-6, characterized in that, The method further includes: separating the reacted materials into solid and liquid phases, and purifying the solid product; Preferably, the purification process includes: performing column chromatography on the solid-phase product, using a mixture of petroleum ether and ethyl acetate with a volume ratio of 2-5:1 as the eluent, and then concentrating the eluted solution under reduced pressure to obtain the crown ether compound.

8. The application of the crown ether compound of claim 1 as an anion recognition agent in the anion recognition process; Preferably, the anion is selected from OH. - SiO3 2- SO4 2- and PO4 3- One or more of them.

9. The application of the crown ether compound of claim 1 as a complexing agent in the process of complexing anions in coal chemical crystalline miscellaneous salts; Preferably, the anion in the coal chemical crystalline miscellaneous salt is selected from OH. - SiO3 2- SO4 2- and PO4 3- One or more of them.

10. A method for treating crystalline impurities in coal chemical industry, characterized in that, The method includes: mixing the crown ether compound of claim 1 with a solution containing coal chemical crystalline miscellaneous salts to carry out a complexation reaction; The anions contained in the coal chemical crystalline miscellaneous salts are selected from OH-. - SiO3 2- SO4 2- and PO4 3- One or more of the following; Preferably, the molar ratio of the crown ether compound to the anion in the coal chemical crystalline miscellaneous salt is 1:0.5-2.5.

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