Fenton-like catalyst for in-situ utilization of inorganic salt in high-salt organic wastewater and application

Abstract

The invention relates to a Fenton-like catalyst for in-situ utilization of inorganic salt in high-salt organic wastewater and application thereof.The Fenton-like catalyst is prepared by the steps that aluminum salt, cobalt salt and carbon nitride are added into n-caprylic alcohol at the same time, the mixture is poured into a reaction kettle after ultrasonic treatment, a hydrothermal reaction is conducted for 15-30 h at the temperature of 140-200 DEG C, and an AlCo / CN double-atom catalyst is obtained after vacuum drying; light energy can be utilized to drive chloride ions to dynamically reconstruct coordination and reduce the spin state of cobalt, and the method is a diatom mediated Fenton-like method which is constructed for the first time and utilizes inorganic salt in high-salt organic wastewater in situ, and shows excellent organic matter removal efficiency. The method shows excellent degradation adaptability to refractory organic pollutants in typical high-salinity organic wastewater in various industries, and provides a method support for subsequent large-scale treatment of the high-salinity organic wastewater.

Description

Technical Field

[0001] The present invention belongs to the field of high-salt organic wastewater treatment, and particularly relates to a Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater and its application. Background Art

[0002] When the total salt content mass fraction of organic wastewater exceeds 1%, it can be called "high-salt organic wastewater", which is one of the difficult-to-treat industrial wastewater types, and has the characteristics of high salinity, high chroma, high concentration and difficult degradation of organic matter, high toxicity and complex composition.

[0003] The traditional cobalt-based dual-atom-mediated photo-Fenton reaction has strong oxidation ability and is an effective treatment technology. However, the traditional high-spin cobalt atoms affect the electron cloud distribution of peroxymonosulfate (PMS) molecules, making PMS more likely to generate free radicals such as sulfate radicals or hydroxyl radicals first, and the generated free radicals will then react with chloride ions to form weakly oxidizing chlorine radicals. In most existing studies, the surface and interface structure of the catalyst is regulated to increase the yield of chlorine radicals in order to reduce the influence of chloride ions on the degradation efficiency. However, as the chlorine radicals increase, the amount of toxic halogenated by-products increases.

[0004] The electron-mediated non-free radical system can avoid the negative effects and secondary hazards of weakly oxidizing chlorine radicals. To construct an electron-mediated system, it is necessary to reduce the cobalt spin, reduce the cobalt electron energy on the basis of ensuring the smooth electron transfer between cobalt and PMS, and then construct a surface-mediated electron transfer system. However, the traditional exogenous methods for regulating the spin state have problems of complex operation and high energy consumption. At present, in the pretreatment stage of high-salt organic wastewater, most attention is paid to the change of active species by salts and its impact on the removal efficiency of pollutants, and less attention is paid to the impact of salts on the structure of the catalyst itself. There are few reports on the in-situ dynamic regulation of the spin state by chloride ions in chloride salts to drive electron-mediated electron transfer. Summary of the Invention

[0005] In view of the above problems, the present invention provides an AlCo / CN Fenton-like catalyst, which changes the cobalt electron structure by regulating the types of dual atoms, in-situ utilizes the inorganic salts in high-salt organic wastewater, and constructs a Fenton-like system with high-salt tolerance and direct electron transfer based on the direct electron transfer of PMS.

[0006] The preparation method of the Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater of the present invention includes the following steps:

[0007] An aluminum salt, a cobalt salt and graphitic carbon nitride (CN) are simultaneously added to n-octanol, ultrasonicated for 3 - 20 min, poured into a reaction kettle for hydrothermal reaction for 15 - 30 h, and dried in vacuum to obtain the AlCo / CN Fenton-like catalyst, and the hydrothermal reaction temperature is 140 - 200 °C.

[0008] Further, the CN is graphitic carbon nitride (g-C3N4).

[0009] Further, the aluminum salt is an aluminum salt such as Al(NO3)3, Al2(SO4)3, and Al(CH3COO)3.

[0010] Further, the cobalt salt is a cobalt salt such as Co(NO3)3, CoSO4, CoCl2, and Co(CH3COO)2.

[0011] Further, the mass ratio of the aluminum salt to the cobalt salt is 1:1 - 1:8.

[0012] Further, the mass ratio of the aluminum salt to the cobalt salt is 1:4.

[0013] Further, the reaction temperature is 160 °C.

[0014] Further, the hydrothermal reaction in the autoclave is carried out for 24 h.

[0015] Further, the ultrasonic time is 10 min.

[0016] Further, the CN is obtained by calcining urea at 400 - 600 °C for 1 - 3 h.

[0017] Another object of the present invention is to provide an AlCo / CN-like Fenton catalyst, which is applied to mediate the degradation of refractory organic pollutants such as high-bromide salts, high-sulfate salts, high-nitrate salts, and high-carbonate salts in a Fenton-like system for high-salt organic wastewater.

[0018] Further, the organic pollutant is one or more of sulfamethoxazole, carbamazepine, tetracycline hydrochloride, 4-chlorophenol, bisphenol A, or atrazine.

[0019] The beneficial effects of the present invention are as follows:

[0020] Utilizing light energy to drive the dynamic reconstruction of coordination of chloride ions and reducing the cobalt spin state, it is the first to construct a dual-atom-mediated Fenton-like method that in-situ utilizes inorganic salts in high-salt organic wastewater, demonstrating excellent organic matter removal efficiency and showing excellent degradation adaptability to refractory organic pollutants in typical high-salt organic wastewater from various industries, providing method support for subsequent large-scale treatment of high-salt organic wastewater. Description of the Drawings

[0021] Figure 1 Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-STEM) of 10Al40Co / CN in Example 3;

[0022] Figure 2XRD patterns of CN of Comparative Example 1, 10Al / CN of Comparative Example 6, 40Co / CN of Comparative Example 7, and 10Al40Co / CN of Example 3;

[0023] Figure 3 FT-IR spectra of CN of Comparative Example 1, 10Al / CN of Comparative Example 6, 40Co / CN of Comparative Example 7, and 10Al40Co / CN of Example 3;

[0024] Figure 4 Synchrotron radiation spectrum of 10Al40Co / CN of Example 3, where Figure 4 a is X-ray absorption near-edge structure, Figure 4 b is extended X-ray absorption fine structure, Figure 4 c is wavelet analysis;

[0025] Figure 5 Efficiencies of Fenton-like degradation of SMX by CN-400 junction of Comparative Example 1, CN of Comparative Example 2, CN-600 junction of Comparative Example 3, CN-1h of Comparative Example 4, and CN-3h of Comparative Example 5;

[0026] Figure 6 Degradation efficiencies of SMX by CN of Comparative Example 2, 10Al / CN of Comparative Example 6, 40Co / CN of Comparative Example 7, and 10Al40Co / CN of Example 3 in the presence of 1008 mM NaCl;

[0027] Figure 7 Degradation efficiencies of SMX by 10Al10Co / CN of Example 1, 10Al20Co / CN of Example 2, 10Al40Co / CN of Example 3, and 10Al80Co / CN of Example 4 in the presence of 1008 mM NaCl;

[0028] Figure 8 Degradation efficiencies of SMX by 10Al40Co / CN of Example 3, 10Al40Co / CN-140 mirror of Example 5, 10Al40Co / CN-180 mirror of Example 5, and 10Al40Co / CN-200 mirror of Example 6 in the presence of 1008 mM NaCl;

[0029] Figure 9 Degradation efficiency of SMX by 10Al40Co / CN of Example 3 in the presence of different NaCl concentrations;

[0030] Figure 10 Degradation efficiencies of SMX by 40Co / CN of Comparative Example 7 and 10Al40Co / CN of Example 3 in the presence of 1008 mM NaCl after adding various scavengers;

[0031] Figure 11 For the degradation efficiency of 10Al40Co / CN in Example 3 in the presence of different kinds of salts for SMX;

[0032] Figure 12 For the degradation efficiency of 10Al40Co / CN in Example 3 for different pollutants in the presence of 1008 mM NaCl. Detailed implementation mode

[0033] In order to make the objectives, technical solutions and advantages of the present invention more clear and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and do not constitute a limitation to the present invention.

[0034] For those not specifying specific techniques or conditions in the embodiments, they shall be carried out according to the techniques or conditions described in the literature in this field or according to the product specifications. For reagents or instruments not indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0035] Comparative Example 1

[0036] 20.0 g of urea was placed in a crucible and placed in a muffle furnace, heated at a rate of 3, and calcined at 500 for 2 h. After the muffle furnace cooled down, carbon nitride was obtained and denoted as CN.

[0037] Comparative Example 2

[0038] 20.0 g of urea was placed in a crucible and placed in a muffle furnace, heated at a rate of 3, and calcined at 400 for 2 h. After the muffle furnace cooled down, carbon nitride was obtained and denoted as CN-400 temperature.

[0039] Comparative Example 3

[0040] 20.0 g of urea was placed in a crucible and placed in a muffle furnace, heated at a rate of 3, and calcined at 600 for 2 h. After the muffle furnace cooled down, carbon nitride was obtained and denoted as CN-600 temperature.

[0041] Comparative Example 4

[0042] 20.0 g of urea was placed in a crucible and placed in a muffle furnace, heated at a rate of 3, and calcined at 500 for 1 h. After the muffle furnace cooled down, carbon nitride was obtained and denoted as CN-1h.

[0043] Comparative Example 5

[0044] 20.0 g of urea was placed in a crucible and placed in a muffle furnace, heated at a rate of 3, and calcined at 500 for 3 h. After the muffle furnace cooled down, carbon nitride was obtained and denoted as CN-3h.

[0045] Comparative Example 6

[0046] 10 mg of Al(NO3)3 and 100 mg of CN prepared in Comparative Example 1 were simultaneously added to 60 mL of n-octanol, sonicated for 10 min, poured into a reaction kettle for reaction, reacted at 160 °C for 24 h, and dried in a vacuum drying oven at 60 °C for 12 h after the reaction. The obtained sample was denoted as 10Al / CN.

[0047] Comparative Example 7

[0048] 40 mg of Co(NO3)3 and 100 mg of CN prepared in Comparative Example 1 were simultaneously added to 60 mL of n-octanol, sonicated for 10 min, poured into a reaction kettle for reaction, reacted at 160 °C for 24 h, and dried in a vacuum drying oven at 60 °C for 12 h after the reaction. The obtained sample was denoted as 40Co / CN.

[0049] Example 1

[0050] 10 mg of Al(NO3)3, 10 mg of Co(NO3)3 and 100 mg of CN of Comparative Example 1 were simultaneously added to 60 mL of n-octanol, sonicated for 10 min, poured into a reaction kettle for reaction, reacted at 160 °C for 24 h, and dried in a vacuum drying oven at 60 °C for 12 h after the reaction. The obtained sample was denoted as 10Al10Co / CN.

[0051] Example 2

[0052] 10 mg of Al(NO3)3, 20 mg of Co(NO3)3 and 100 mg of CN of Comparative Example 1 were simultaneously added to 60 mL of n-octanol, sonicated for 10 min, poured into a reaction kettle for reaction, reacted at 160 °C for 24 h, and dried in a vacuum drying oven at 60 °C for 12 h after the reaction. The obtained sample was denoted as 10Al20Co / CN.

[0053] Example 3

[0054] 10 mg of Al(NO3)3, 40 mg of Co(NO3)3 and 100 mg of CN of Comparative Example 1 were simultaneously added to 60 mL of n-octanol, sonicated for 10 min, poured into a reaction kettle for reaction, reacted at 160 °C for 24 h, and dried in a vacuum drying oven at 60 °C for 12 h after the reaction. The obtained sample was denoted as 10Al40Co / CN.

[0055] Example 4

[0056] 10 mg of Al(NO3)3, 80 mg of Co(NO3)3 and 100 mg of CN of Comparative Example 1 were simultaneously added to 60 mL of n-octanol, sonicated for 10 min, poured into a reaction kettle for reaction, reacted at 160 °C for 24 h, and dried in a vacuum drying oven at 60 °C for 12 h after the reaction. The obtained sample was denoted as 10Al80Co / CN.

[0057] Example 5

[0058] 10 mg of Al(NO3)3, 80 mg of Co(NO3)3 and 100 mg of the CN of Comparative Example 1 were simultaneously added to 60 mL of n-octanol, ultrasonicated for 10 min, poured into a reaction kettle for reaction, reacted at 160 °C for 24 h, and then dried in a vacuum drying oven at 60 °C for 12 h. The obtained sample was denoted as 10Al40Co / CN-140.

[0059] Example 6

[0060] 10 mg of Al(NO3)3, 80 mg of Co(NO3)3 and 100 mg of the CN of Comparative Example 1 were simultaneously added to 60 mL of n-octanol, ultrasonicated for 10 min, poured into a reaction kettle for reaction, reacted at 180 °C for 24 h, and then dried in a vacuum drying oven at 60 °C for 12 h. The obtained sample was denoted as 10Al40Co / CN-180.

[0061] Example 7

[0062] 10 mg of Al(NO3)3, 80 mg of Co(NO3)3 and 100 mg of the CN of Comparative Example 1 were simultaneously added to 60 mL of n-octanol, ultrasonicated for 10 min, poured into a reaction kettle for reaction, reacted at 200 °C for 24 h, and then dried in a vacuum drying oven at 60 °C for 12 h. The obtained sample was denoted as 10Al80Co / CN-200.

[0063] The AC-STEM of 10Al40Co / CN of Example 3 is as Figure 1 shown. The dual-atom pairs in 10Al40Co / CN are uniformly dispersed and accompanied by bright spots.

[0064] As Figure 2 shown, the XRD patterns of the CN of Comparative Example 1, 10Al / CN of Comparative Example 6, 40Co / CN of Comparative Example 7 and 10Al40Co / CN of Example 3 show diffraction peaks at 12.70 and 26.70, corresponding to the (100) and (002) planes of CN. Due to the low content of Al and Co elements, the diffraction peaks of Al and Co were not detected in the XRD patterns of 10Al / CN of Comparative Example 6, 40Co / CN of Comparative Example 7 and 10Al40Co / CN of Example 3.

[0065] As Figure 3 shown, the FT-IR spectra of the CN of Comparative Example 1, 10Al / CN of Comparative Example 6, 40Co / CN of Comparative Example 7 and 10Al40Co / CN of Example 3 all show -NH2 / =NH2, C=N / C-N and -NH2 and =NH. -NH2 / =NH2 corresponds to 809 cm -1The peak of C=N / C-N corresponds to 1211-1647 cm -1 The broad peak, -NH2 and =NH correspond to 3047-3400 cm -1 The peak of

[0066] As Figure 4 shown in a, the cobalt absorption edge in the K-edge XANES of 10Al40Co / CN in Example 3 indicates that the oxidation state of cobalt is between +2 and +3. As Figure 4 shown in b, the EXAFS spectrum shows that the peaks at correspond to Co-N, Co-Al, and Al-N bonds respectively, as Figure 4 shown in c, the WT contour also proves this. The above results prove that the AlCo / CN dual-atom catalyst was successfully constructed.

[0067] Application Example 1

[0068] The application of CN in Comparative Examples 1-5, 10Al / CN in Comparative Example 6, 40Co / CN in Comparative Example 7, and AlCo / CN in Examples 1-7 for the treatment of various refractory organic pollutants in high-salt organic wastewater by the Fenton-like process.

[0069] First, 4.0 mg of CN in Comparative Examples 1-5, 10Al / CN in Comparative Example 6, 40Co / CN in Comparative Example 7, and AlCo / CN in Examples 1 to 7 were added to 20 mL of SMX, CBZ, TCH, 4-CP, BPA, ATZ, CBZ (0.04 mM), and stirred in the dark for 30 min to reach the adsorption-desorption equilibrium.

[0070] Then, the reaction was excited with 1.0 mM of PMS. 2.0 mL of the sample was collected every 1 minute and filtered through a 0.22 μm filter membrane, and then 1 mM of Na2S2O3 was added. The concentration of various organic pollutants was measured using a Thermo Fisher liquid chromatograph.

[0071] The results of the Fenton-like degradation of SMX by CN-400 in Comparative Example 1, CN in Comparative Example 2, CN-600 in Comparative Example 3, CN-1h in Comparative Example 4, and CN-3h in Comparative Example 5 are as Figure 5 shown. The degradation efficiency of SMX by CN in Comparative Example 2 was 83.7% after 30 minutes of the Fenton-like reaction in the presence of 1008 mM NaCl, higher than that of CN-400 in Comparative Example 1 (75.3%), CN-600 in Comparative Example 3 (62.2%), CN-1h in Comparative Example 4 (71.3%), and CN-3h in Comparative Example 5 (80.2%) for the degradation of SMX.

[0072] The degradation efficiency of CN of Comparative Example 2, 10Al / CN of Comparative Example 6, 40Co / CN of Comparative Example 7, and 10Al40Co / CN of Example 3 for SMX in the presence of 1008 mM NaCl is as Figure 6 shown. The efficiency of Fenton-like degradation of SMX by 10Al40Co / CN in Example 3 is 96.4%, which is higher than that of CN (84.0%) in Comparative Example 2, 10Al / CN (88.4%) in Comparative Example 6, and 40Co / CN (86.0%) in Comparative Example 7, respectively. The above shows that the synergistic effect between Al and Co dual atoms can promote the degradation of SMX.

[0073] The degradation efficiency of 10Al10Co / CN of Example 1, 10Al20Co / CN of Example 2, 10Al40Co / CN of Example 3, and 10Al80Co / CN of Example 4 for SMX in the presence of 1008 mM NaCl is as Figure 7 shown. The efficiency of Fenton-like degradation of SMX by 10Al40Co / CN in Example 3 is 96.4%, which is higher than that of 10Al10Co / CN (95.2%) in Example 1, 10Al20Co / CN (92.5%) in Example 2, and 10Al80Co / CN (91.6%) in Example 4, respectively. It shows that the optimal ratio of Al and Co dual atoms is 1:4.

[0074] The degradation efficiency of 10Al40Co / CN of Example 3, 10Al40Co / CN-1404 of Example 5, 10Al40Co / CN-180 dye of Example 5, and 10Al40Co / CN-200 dye of Example 6 for SMX in the presence of 1008 mM NaCl is as Figure 8 shown. The efficiency of Fenton-like degradation of SMX by 10Al40Co / CN in Example 3 is 96.4%, which is higher than that of 10Al40Co / CN-140 (92.2%) in Example 5, 10Al40Co / CN-180 (94.7%) in Example 6, and 10Al40Co / CN-200 (94.4%) in Example 7, respectively. The above shows that the optimal temperature for the preparation of the AlCo / CN dual-atom catalyst is 160.

[0075] The degradation efficiency of 10Al40Co / CN of Example 3 for SMX in the presence of different NaCl concentrations is as Figure 9 shown. The efficiency of Fenton-like degradation of SMX by 10Al40Co / CN in Example 3 is 84.0%. As the NaCl concentration increases from 0 to 50 mM, the degradation efficiency of SMX decreases to 73.0%. As the NaCl concentration increases from 50 mM to 150 mM, the degradation efficiency of SMX increases to 80.1% and as the NaCl concentration gradually increases to 1000 mM NaCl, the degradation efficiency of SMX increases to 96.4%.

[0076] The degradation efficiency of SMX by 40Co / CN of Comparative Example 7 and 10Al40Co / CN of Example 3 after adding various scavengers in the presence of 1008 mM NaCl is as Figure 10 shown. After adding isopropanol (IPA), methanol (MeOH), ammonium sulfate ((NH4)2SO4), sodium acetate (CH3COONa), tert-butanol (TBA), methyl phenyl sulfoxide (PMSO), carotene (β-carotene), acetone, and sodium bicarbonate (NaHCO3) to the 40Co / CN Fenton system, the degradation efficiency of SMX decreased significantly. However, after adding IPA, MeOH, (NH4)2SO4, CH3COONa, TBA, PMSO, β-carotene, acetone, and NaHCO3 to the 10Al40Co / CN Fenton system, the degradation efficiency of SMX did not decrease significantly, indicating that surface-mediated electron transfer is the main pathway in the Fenton-like system based on 10Al40Co / CN.

[0077] The degradation efficiency of SMX by 10Al40Co / CN of Example 3 in the presence of different salts is as Figure 11 shown. The degradation efficiency of SMX by 10Al40Co / CN of Example 3 through Fenton-like reaction in the presence of 1008 mM NaCl is 96.4%, in the presence of 1008 mM NaBr is 95.5%, in the presence of 1008 mM Na2SO4 is 94.5%, in the presence of 1008 mM NaNO3 is 97.6%, and in the presence of 1008 mM Na2CO3 is 94.7%.

[0078] In other examples, the only difference from Example 3 is that Al(NO3)3 is replaced by Al2(SO4)3, and the degradation efficiency of the obtained catalyst for SMX through Fenton-like reaction in the presence of 1008 mM NaCl is 93.4%. When Al(NO3)3 is replaced by Al(CH3COO)3 in the obtained catalyst, the degradation efficiency of SMX through Fenton-like reaction in the presence of 1008 mM NaCl is 95.1%.

[0079] In other examples, the only difference from Example 3 is that Co(NO3)3 is replaced by CoSO 4，The efficiency of the obtained catalyst for the degradation of SMX by Fenton-like in the presence of 1008 mM NaCl is 96.2%. When Co(NO3)3 is replaced by CoCl2, the efficiency of the obtained catalyst for the degradation of SMX by Fenton-like in the presence of 1008 mM NaCl is 94.7%. When Co(NO3)3 is replaced by Co(CH3COO)2, the efficiency of the obtained catalyst for the degradation of SMX by Fenton-like in the presence of 1008 mM NaCl is 92.6%.

[0080] Application Example 2

[0081] Application of 10Al40Co / CN in Example 3 for the Fenton treatment of various organic pollutants in high-chloride organic wastewater.

[0082] First, 4.0 mg of 10Al40Co / CN in Example 3 was added to 20.0 mL of an aqueous solution of 0.04 mM sulfamethoxazole (SMX), carbamazepine (CBZ), tetracycline hydrochloride (TCH), 4-chlorophenol (4-CP), bisphenol A (BPA), and atrazine (ATZ), and stirred for 30 min in the dark to achieve adsorption-desorption equilibrium. Then, 1.0 mM PMS was used to initiate the reaction. During the reaction, 2.0 mL of the sample was collected every 1 minute and filtered through a 0.22 μm filter membrane, and then 1.0 mM of Na2S2O3 was added. The concentrations of various organic pollutants were determined using a Thermo Fisher liquid chromatograph.

[0083] The efficiency of 10Al40Co / CN in Example 3 for the degradation of different pollutants in the presence of 1008 mM NaCl is as Figure 12 shown. The efficiency of 10Al40Co / CN in Example 3 for the degradation of SMX by Fenton-like in the presence of 1008 mM NaCl is 96.4%, the efficiency for the degradation of CBZ by Fenton-like in the presence of 1008 mM NaCl is 100%, the efficiency for the degradation of TCH by Fenton-like in the presence of 1008 mM NaCl is 100%, the efficiency for the degradation of 4-CP by Fenton-like in the presence of 1008 mM NaCl is 99.9%, the efficiency for the degradation of BPA by Fenton-like in the presence of 1008 mM NaCl is 100%, and the efficiency for the degradation of ATZ by Fenton-like in the presence of 1008 mM NaCl is 99.9%. The above results indicate that the dual-atom-mediated Fenton-like has good degradation adaptability to different types of organic pollutants in the presence of high salt.

[0084] In the present invention, chloride ions in high salt such as chloride salt can withdraw electrons, change the orbital distribution, reduce the in-situ spin state, and promote the construction of an electron-mediated oxidation system.

[0085] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. An in-situ Fenton-like catalyst for utilizing inorganic salts in high-salt organic wastewater, characterized in that, It includes the following steps: Add Al(NO3)3, Co(NO3)3 and CN into n-octanol simultaneously, ultrasonicate for 3 - 20 min, pour it into a reaction kettle for hydrothermal reaction for 15 - 30 h, and obtain the AlCo / CN dual-atom catalyst after vacuum drying, with the reaction temperature being 140 - 200 °C.

2. The preparation method of the Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater according to claim 1, wherein, The mass ratio of the described Al(NO3)3 to Co(NO3)3 is 1:1 - 1:

8.

3. The preparation method of the Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater according to claim 1, wherein, The mass ratio of the described Al(NO3)3 to Co(NO3)3 is 1:

4.

4. The preparation method of the Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater according to claim 1, characterized in that, The described reaction temperature is 160 °C.

5. The preparation method of the Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater according to claim 1, characterized in that The hydrothermal reaction in the described reaction kettle is for 24 h.

6. The preparation method of the Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater according to claim 1, characterized in that The described ultrasonication time is 10 min.

7. The preparation method of the Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater according to claim 1, characterized in that, The described CN is obtained by calcining urea at a temperature of 400 - 600 °C for 2 h.

8. An in-situ Fenton-like catalyst for utilizing inorganic salts in high-salt organic wastewater, characterized in that, It is obtained by the preparation method of the AlCo / CN dual-atom Fenton-like catalyst described in claim 1.

9. The Fenton-like catalyst for in-situ utilization of inorganic salts in high-salt organic wastewater according to claim 8, wherein The described Fenton-like catalyst is used to mediate the degradation of organic pollutants in the Fenton-like system of high-salt organic wastewater.

10. The in-situ Fenton-like catalyst for utilizing inorganic salts in high-salt organic wastewater according to claim 8, wherein: The described organic pollutants are one or several of sulfamethoxazole, carbamazepine, tetracycline hydrochloride, 4-chlorophenol, bisphenol A or atrazine.

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