Solid adsorbent, method for preparing the same, and use thereof

Abstract

The application discloses a kind of solid adsorbent and its preparation method and application.The application is dissolved in anhydrous ethanol with organic amine, 10-25 ℃ is stirred and dissolved, and forms homogeneous organic amine solution;Metal ion modified porous material is added to the organic amine solution, and is fully stirred and immersed at 10-25 ℃, and the stirring time is 5-10 h, and the solid adsorbent is obtained after filtration and drying.The solid adsorbent of the application can effectively remove organic matter in wastewater, especially the adsorption efficiency of oxygen-containing organic matter such as phenol and phenethyl alcohol is higher.The application realizes the continuous operation of wastewater treatment, so that the wastewater treatment efficiency is higher;Adsorbent can be regenerated by solvent desorption, and soaking solvent can be reused by distillation method, which avoids resource waste.

Description

Technical Field

[0001] This invention belongs to the field of chemical production, specifically relating to a solid adsorbent, its preparation method, and its application. Background Technology

[0002] The production process of dicumyl peroxide (DCP) mainly involves condensation, washing, concentration, crystallization, and drying. In industrial production, perchloric acid is mostly used as a catalyst in the condensation process. During the reaction, many byproducts are generated, such as aromatic organic compounds like phenol, acetophenone, and AMS. To avoid the impact of byproducts on the quality of the crystalline product, these organic compounds need to be removed by alkaline washing and water washing processes. This process generates a large amount of wastewater with high salt and high COD content, which increases treatment costs and causes raw material loss.

[0003] Currently, the main methods for wastewater treatment in the DCP production process are as follows:

[0004] (1) Using the acidification extraction method, the pH of the wastewater is first adjusted to acidic, and the extractant is added and mixed thoroughly before separation. This allows the organic matter in the wastewater to be enriched in the oil layer, and the organic matter in the oil layer is recovered. The aqueous phase is then discharged to the wastewater treatment plant after distillation. This method has limited wastewater treatment capacity and is cumbersome, making it unsuitable for large-scale wastewater recycling.

[0005] (2) The wastewater from the DCP production unit was biodegraded using a series connection of a primary facultative anaerobic biochemical tank and a secondary aerobic biochemical tank. However, the bacteria required to meet the high requirements for metal and impurity content in the wastewater, and further treatment was needed before biodegradation, which increased the cost.

[0006] (3) Using adsorption, β-zeolite molecular sieve was used as the adsorbent to recover cumene from the wastewater during the crystallization process. This adsorbent was not modified and had limited adsorption capacity for other organic matter in the wastewater. Furthermore, the adsorbent was unstable and the adsorption effect was poor.

[0007] The above methods are all intermittent operations, which are inefficient. The effective means used are also difficult to reuse, resulting in high costs. Furthermore, the wastewater treated by these methods is difficult to regenerate, and the goal of reducing wastewater discharge has not been achieved.

[0008] Therefore, it is imperative to seek efficient wastewater treatment methods. Summary of the Invention

[0009] Objective of the Invention: The objective of this invention is to address the shortcomings of existing technologies by providing a solid adsorbent, its preparation method, and its applications. The solid adsorbent of this invention can be used for the treatment of organic wastewater, particularly for the treatment of washing wastewater and similar wastewater from DCP production.

[0010] Technical solution: The objective of this invention is achieved through the following technical solution:

[0011] This invention provides a method for preparing a solid adsorbent, comprising the following steps:

[0012] (1) Dissolve the organic amine in anhydrous ethanol and stir at 10-25℃ to form a homogeneous organic amine solution;

[0013] (2) Add the metal ion-modified porous material to the organic amine solution prepared in step (1), stir and impregnate it thoroughly at 10-25°C for 5-10 hours, filter and dry to obtain the solid adsorbent.

[0014] Preferably, in step (2), the metal ion-modified porous material is prepared by the following method:

[0015] (1) Weigh out soluble salts containing metals Zn, Cu, and Mg, stir in water until dissolved, and form a metal salt solution with a mass fraction of 1%-20%;

[0016] (2) Take the calcined porous material and immerse it in the metal salt solution prepared in step (1). The immersion temperature is 10-25℃ and the immersion time is 5-10h. Filter and dry to obtain the metal ion modified porous material.

[0017] More preferably, in step (1), the soluble salt includes one or more of the following: sulfate, hydrochloride, nitrate, acetate, phosphate, formate or chlorate containing metals Zn, Cu, or Mg.

[0018] More preferably, the calcined porous material is selected from one or more of the following: XDA series macroporous resins, SBA-15, SBA-16, MCM-41, KIT-resin, carbon-based molecular sieves, activated carbon, mesoporous silica, aerogel, columnar clay, alumina, phosphates, or MOFs; the mass ratio of the porous material to the metal salt solution is 0.1-0.25.

[0019] More preferably, in step (2), the calcination refers to calcination under N2 atmosphere protection to remove impurities, the calcination temperature is 200-400℃, and the calcination time is 6-8h.

[0020] Preferably, the organic amine is selected from one or more of polyethyleneimine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethylenediamine, ethanolamine, diethanolamine, or N-methylethylene glycolamine.

[0021] Preferably, the concentration of the organic amine solution is 5%-25%, and the mass ratio of the metal ion-modified porous material to the organic amine solution is 0.01-0.2.

[0022] The present invention also provides a solid adsorbent prepared by the preparation method described above.

[0023] The present invention also provides the application of the solid adsorbent in the treatment of organic wastewater, wherein the solid adsorbent is filled into an adsorption tower to achieve the treatment of organic wastewater.

[0024] This invention provides an organic wastewater treatment device, including an adsorption unit, an adsorbent regeneration unit, and a solvent recovery unit.

[0025] This invention employs the aforementioned organic wastewater treatment device and provides a process for treating organic wastewater using the solid adsorbent. The organic wastewater is pumped into an adsorption tower filled with the solid adsorbent. After adsorption treatment, it enters a storage tank at the bottom of the tower and is then transported via pipeline to a production unit for reuse. The used solid adsorbent enters an adsorbent regeneration reactor, where it is regenerated through solvent desorption. The desorbed solvent enters a storage tank and is then pumped into a solvent recovery tower for treatment. The recovered solvent is obtained at the top of the tower and recycled back to the regeneration reactor for reuse, while organic matter is obtained at the bottom of the tower.

[0026] Using the process of this invention, the organic wastewater after adsorption can be recycled back to the process section for continued use, thereby reducing the amount of wastewater discharged.

[0027] Preferably, the present invention employs a continuous adsorption method to achieve continuous operation of wastewater treatment.

[0028] Preferably, the filling height of the adsorption layer inside the adsorption tower is 70-250 mm, and the porosity is 20-80%.

[0029] Preferably, the operating temperature inside the adsorption tower is 20-30℃, and the material volume hourly space velocity is 0.125-1 min. -1 .

[0030] The stirring rate in the regeneration vessel of the adsorption tower is 120-360 r / min;

[0031] The desorption solvent is selected from methanol, ethanol, or ethylene glycol;

[0032] The solvent recovery tower is a distillation tower with 3-45 effective trays, a reflux ratio of 2.0-6.0, and a distillation ratio of 0.6-0.95.

[0033] The porosity within the adsorbent tower directly affects the quality of the output; a higher porosity results in a lower organic matter removal rate. To ensure effective adsorption, the porosity should be 20-80%, and the filling height of the adsorption layer should be 70-250 mm.

[0034] Wastewater is pumped into the adsorption tower. The upper part of the tower employs a liquid redistribution device, which can be either a showerhead type or an overflow tray type. The adsorption effect of the tower on wastewater is directly proportional to the residence time of the wastewater within the tower. However, excessively long residence times will reduce production capacity. Therefore, to balance adsorption efficiency, the material volume hourly space velocity (VHSV) is controlled at 0.125-1 min. -1 .

[0035] The present invention found that there is no obvious positive correlation between adsorption temperature and adsorption effect. In order to reduce energy consumption, the operating temperature inside the adsorption tower can be selected as 20-30℃.

[0036] To achieve adsorbent regeneration, the adsorbent regeneration unit uses solvent desorption to recover the organic matter. Common solvents such as methanol and petroleum ether can be selected. Considering the energy consumption of subsequent solvent recovery, small molecule alcohols such as methanol, ethanol, and ethylene glycol with lower boiling points are preferred.

[0037] In addition, to ensure that the organic matter is fully desorbed, the stirring rate in the adsorption tower regeneration vessel is 120-360 r / min, and the stirring time is 2-3 hours. After that, the liquid enters the solvent recovery tower through the outlet.

[0038] The solvent recovery unit uses a distillation column to recover the solvent. To reduce energy consumption while ensuring separation efficiency, the preferred number of effective trays in the column is 5-20, and the reflux ratio is 2.0-4.0. The distillation ratio is adjusted to a range of 0.6-0.95 depending on the solvent content in the leaching solution. The distillation column can operate under atmospheric or reduced pressure; the device of this invention preferably operates under reduced pressure to lower the operating temperature and avoid safety issues.

[0039] Beneficial effects:

[0040] 1. This invention enhances the adsorption efficiency of organic matter, especially oxygen-containing organic matter, in wastewater by dual modification of existing porous carriers to strengthen intermolecular interactions. First, metal ions are introduced through an excess impregnation method to exchange ions with cations in the carrier framework, increasing surface acidity. During subsequent loading, this further enhances the interaction between the active component and the carrier, thereby increasing the content of the active component. Additionally, the larger radius of the metal ions modifies the carrier pores, further enhancing its adsorption capacity. Qualitative and quantitative analysis of organic matter in wastewater reveals a high content of oxygen-containing organic matter. However, traditional adsorbents primarily rely on van der Waals forces, resulting in low adsorption efficiency. Considering that oxygen-containing organic matter can form hydrogen bonds, a strong interaction force, this invention introduces amino groups onto the carrier surface to improve the adsorption capacity for organic matter such as phenol and phenylethanol.

[0041] 2. This invention utilizes strong intermolecular interactions, namely hydrogen bonds, to effectively remove organic matter from wastewater, especially oxygen-containing organic matter such as phenol and phenylethanol, with higher adsorption efficiency.

[0042] 3. This invention enables continuous operation of wastewater treatment, resulting in higher wastewater treatment efficiency; the adsorbent can be regenerated through solvent desorption, and the soaking solvent can be reused through distillation, thus avoiding resource waste.

[0043] 4. The wastewater treated by this invention can be recycled to the water washing unit in the production device, which can reduce the amount of production wastewater discharge by about 1 / 3 to 2 / 3. Attached Figure Description

[0044] Figure 1 This is a flow chart of an organic wastewater treatment process.

[0045] Among them, 1-washing tank, 2-stirring paddle, 3, 8, 10, 15, 17-storage tank, 4, 7, 11, 14, 16-heat exchanger, 5, 12-vacuum pump, 6-adsorption tower, 9-adsorbent regeneration tank, 13-solvent recovery tower, 18-adsorbent activation tank. Detailed Implementation

[0046] The technical solution of the present invention will be described in detail below through specific embodiments, but the scope of protection of the present invention is not limited to the embodiments described.

[0047] This invention provides a process for treating organic wastewater. The process utilizes a wastewater treatment device, including an adsorption unit, an adsorbent regeneration unit, and a solvent recovery unit. The organic wastewater treatment process flow of this invention is as follows: Figure 1 As shown.

[0048] Organic wastewater from the washing unit is stored in storage tank 3. After being cooled to 10-25°C by heat exchanger 4, it is pumped into adsorption tower 6 filled with the adsorbent of this invention via vacuum pump. The organic wastewater after adsorption treatment is stored in storage tank 8 and then transported to the washing unit via pipeline for recycling. After a period of use, the adsorbent with decreased adsorption efficiency is transferred to adsorbent regeneration tank 9 (equipped with a stirring paddle) through the discharge device at the bottom of the adsorption tower. The desorption solvent enters from the top of adsorbent regeneration tank 9, and the desorption solvent and adsorbent are stirred and mixed in the tank to regenerate the adsorbent. The desorption solvent continues to enter solvent recovery tower 13. After continuous distillation, the recovered solvent is obtained in storage tank 15 (discharge tank) at the top of the tower and can be transported to the adsorbent regeneration tank for recycling via pipeline. High-boiling-point organic compounds are obtained in storage tank 17 at the bottom of the tower.

[0049] In this embodiment of the invention, the organic wastewater in the washing unit comes from the wastewater generated during the DCP production process.

[0050] The adsorption tower used in this embodiment of the invention has an adsorption layer with a filling height of 120 mm and a porosity of 60%.

[0051] In this embodiment of the invention, the solvent recovery tower is a distillation tower with 10 effective trays, a reflux ratio of 2.0, and a distillation ratio of 0.9.

[0052] The porous materials described in the following examples are all commercially available products. The XDA-4 resin has a particle size of 0.49-0.69 mm and a density of 0.68 g / cm³. 3 The purity of the mesoporous silica is 99%, and its specific surface area is 511 m². 2 / g, Total pore volume: 0.806cm³ 3 / g, average pore size: 6.31nm; specific surface area of ​​mesoporous alumina: 144.8m² 2 / g, Total pore volume: 0.260cm³ 3 / g, average pore size: 7.19nm.

[0053] Example 1

[0054] A soluble salt containing metallic Zn, ZnCl2, was dissolved in deionized water to form a 2% (w / w) metal salt solution. Then, XDA-4 resin porous material, calcined at 200°C for 6 hours in a N2 atmosphere, was stirred and impregnated in the ZnCl2 solution with a mass ratio of porous material to metal salt solution of 0.1. After stirring at 25°C for 10 hours, the mixture was filtered and vacuum dried to obtain the Zn-modified porous material. Next, ethylenediamine was dissolved in anhydrous ethanol to form a 7% organic amine solution. Finally, the Zn-modified porous material was placed in the organic amine solution with a mass ratio of Zn-modified porous material to organic amine solution of 0.2. After stirring and impregnation at 10°C for 9 hours, the adsorbent was filtered out and then vacuum dried to obtain a solid adsorbent.

[0055] In the adsorption unit, the adsorbent is the prepared solid adsorbent, and the material has a volume hourly space velocity (VHSV) of 0.125 min⁻¹. -1 The material enters the adsorption tower at an adsorption pressure of 0 MPa and an adsorption temperature of 20°C. After adsorption is complete, the first adsorbed material is obtained. In the adsorbent regeneration unit, the solvent is methanol, the stirring rate is 240 r / min, the reaction temperature is 20°C, and the stirring time is 2 h.

[0056] Example 2

[0057] A soluble salt containing metallic Mg, Mg(NO3)2, was dissolved in deionized water to form a 15% (w / w) metal salt solution. Mesoporous silica, calcined at 200°C for 6 hours in a N2 atmosphere, was then impregnated in the Mg(NO3)2 solution with stirring. The mass ratio of the porous material to the metal salt solution was 0.2. After stirring at 15°C for 6 hours, the mixture was filtered and vacuum dried to obtain a Mg-modified porous material. Ethanolamine was then dissolved in anhydrous ethanol to form a 25% (w / w) organic amine solution. Finally, the Mg-modified porous material was placed in the organic amine solution with a mass ratio of 0.02. The mixture was stirred and impregnated at 25°C for 5 hours, and the adsorbent was filtered out and vacuum dried to obtain a solid adsorbent.

[0058] In the adsorption unit, the adsorbent is the prepared solid adsorbent, and the material has a volume hourly space velocity (VHSV) of 0.15 min⁻¹. -1 The material enters the adsorption tower at an adsorption pressure of 0 MPa and an adsorption temperature of 20°C. After adsorption is complete, the second adsorbed material is obtained. In the adsorbent regeneration unit, the solvent is methanol, the stirring rate is 240 r / min, the reaction temperature is 20°C, and the stirring time is 2 h.

[0059] Example 3

[0060] CuCl2, a soluble salt containing metallic Cu, was dissolved in deionized water to form a 20% (w / w) metal salt solution. XDA-4 resin porous material, calcined at 200°C for 8 hours in a N2 atmosphere, was then stirred and impregnated in the CuCl2 solution with a mass ratio of porous material to metal salt solution of 0.25. After stirring at 10°C for 10 hours, the mixture was filtered and vacuum dried to obtain Cu-modified porous material. Diethanolamine was then dissolved in anhydrous ethanol to form a 20% (w / w) organic amine solution. Finally, the Cu-modified porous material was placed in the organic amine solution with a mass ratio of Cu-modified porous material to organic amine solution of 0.1. The mixture was stirred and impregnated at 25°C for 10 hours, and the adsorbent was filtered out and vacuum dried to obtain a solid adsorbent.

[0061] In the adsorption unit, the adsorbent is the prepared solid adsorbent, and the material has a volume hourly space velocity (VHSV) of 0.75 min⁻¹. -1 The material enters the adsorption tower at an adsorption pressure of 0 MPa and an adsorption temperature of 20°C. After adsorption is complete, the second adsorbed material is obtained. In the adsorbent regeneration unit, the solvent is methanol, the stirring rate is 240 r / min, the reaction temperature is 20°C, and the stirring time is 2 h.

[0062] Example 4

[0063] CuSO4, a soluble salt containing metallic Cu, was dissolved in deionized water to form a 6% (w / w) metal salt solution. Mesoporous alumina calcined at 200°C for 8 hours in a N2 atmosphere was then impregnated in the CuSO4 solution with stirring. The mass ratio of the porous material to the metal salt solution was 0.25. After stirring at 25°C for 10 hours, the mixture was filtered and vacuum dried to obtain a Cu-modified porous material. Diethylenetriamine was then dissolved in anhydrous ethanol to form a 25% organic amine solution. Finally, the Cu-modified porous material was placed in the organic amine solution with a mass ratio of 0.2 (w / w). After stirring and impregnation at 25°C for 8 hours, the adsorbent was filtered out and vacuum dried to obtain a solid adsorbent.

[0064] In the adsorption unit, the adsorbent is the prepared target adsorbent, and the material has a volume hourly space velocity (VHSV) of 1 min. -1 The material enters the adsorption tower at an adsorption pressure of 0 MPa and an adsorption temperature of 20°C. After adsorption is complete, the fourth adsorbed material is obtained. In the adsorbent regeneration unit, the solvent is methanol, the stirring rate is 240 r / min, the reaction temperature is 20°C, and the stirring time is 2 h.

[0065] Example 5

[0066] A soluble salt containing metallic Zn, Zn(NO3)2, was dissolved in deionized water to form an 18% metal salt solution. XDA-4 resin, calcined at 200°C for 6 hours in a N2 atmosphere, was then impregnated in the Zn(NO3)2 solution with stirring. The mass ratio of the porous material to the metal salt solution was 0.25. After stirring at 15°C for 5 hours, the mixture was filtered and vacuum dried to obtain the Zn-modified porous material. Ethylenediamine was then dissolved in anhydrous ethanol to form a 25% organic amine solution. Finally, the Zn-modified porous material was placed in the organic amine solution with a mass ratio of 0.2. The mixture was stirred and impregnated at 25°C for 8 hours, and the adsorbent was filtered out and vacuum dried to obtain a solid adsorbent.

[0067] In the adsorption unit, the adsorbent is the prepared target adsorbent, and the material has a volume hourly space velocity (VHSV) of 0.125 min⁻¹. -1 The material enters the adsorption tower at an adsorption pressure of 0 MPa and an adsorption temperature of 30°C. After adsorption is complete, the fifth adsorbed material is obtained. In the adsorbent regeneration unit, the solvent is methanol, the stirring rate is 240 r / min, the reaction temperature is 20°C, and the stirring time is 2 h.

[0068] Example 6

[0069] A soluble salt containing metallic Mg, MgCl2, was dissolved in deionized water to form a 5% metal salt solution. XDA-4 resin, calcined at 200°C for 6 hours in a N2 atmosphere, was then impregnated in the MgCl2 solution with stirring. The mass ratio of porous material to metal salt solution was 0.25. After stirring at 25°C for 10 hours, the mixture was filtered and vacuum dried to obtain Mg-modified porous material. Ethylenediamine was then dissolved in anhydrous ethanol to form a 25% organic amine solution. Finally, the Mg-modified porous material was placed in the organic amine solution with a mass ratio of 0.18. The mixture was stirred and impregnated at 25°C for 8 hours, and the adsorbent was filtered out and vacuum dried to obtain a solid adsorbent.

[0070] In the adsorption unit, the adsorbent is the prepared target adsorbent, and the material has a volume hourly space velocity (VHSV) of 0.65 min⁻¹. -1 The material enters the adsorption tower at an adsorption pressure of 0 MPa and an adsorption temperature of 25°C. After adsorption is complete, the sixth adsorbed material is obtained. In the adsorbent regeneration unit, the solvent is methanol, the stirring rate is 300 r / min, the reaction temperature is 20°C, and the stirring time is 2 h.

[0071] Example 7

[0072] In the adsorption unit, the adsorbent is the same as that used in Example 1. After solvent desorption, the adsorbent is recycled back to the adsorption process, and the material has a volume hourly space velocity (VHSV) of 0.125 min⁻¹. -1 The material enters the adsorption tower at an adsorption pressure of 0 MPa and an adsorption temperature of 30°C. After adsorption is complete, the 7th adsorbed material is obtained. In the adsorbent regeneration unit, the solvent is methanol, the stirring rate is 240 r / min, the reaction temperature is 20°C, and the stirring time is 2 h.

[0073] Comparative Example 1

[0074] The wastewater was treated by acid extraction using 0.1 mol / L hydrochloric acid at a concentration of 5%. After the oil and water separated, the aqueous phase was extracted and recovered using cumene as the extractant. The oil-to-water ratio was 0.9:1. After standing for 1 hour, the eighth purified material was obtained.

[0075] Comparative Example 2

[0076] The wastewater was treated by acid extraction using 0.1 mol / L hydrochloric acid at a concentration of 5%. After the oil and water separated, the aqueous phase was extracted and recovered using acetophenone as the extractant and an oil-to-water ratio of 0.9:1. After standing for 1 hour, the 9th purified material was obtained.

[0077] Comparative Example 3

[0078] The wastewater was treated by acid extraction using 0.1 mol / L hydrochloric acid at a concentration of 5%. After the oil and water separated, the aqueous phase was extracted and recovered using isooctane as the extractant and an oil-to-water ratio of 0.9:1. After standing for 1 hour, the 10th purified material was obtained.

[0079] The component analysis results of the purified materials obtained from each embodiment and comparative example are listed in Tables 1 and 2.

[0080] Table 1 Results of the Examples

[0081] wastewater sample Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Phenol / ppm 645 39 47 40 45 31 42 40 Phenylacetyl alcohol / ppm 92 5 5 5 6 0 5 6 Acetophenone / ppm 73 0 0 0 0 0 0 0 DMBA / ppm 1065 32 35 38 52 27 40 30 CHP / ppm 150 0 0 0 0 0 0 0 CM / ppm 645 239 242 259 275 214 235 243 Organic matter removal rate / 88.20％ 87.68％ 87.48％ 87.72％ 89.19％ 88.37％ 88.05％

[0082] Table 2 Comparative results

[0083] Wastewater as is Comparative Example 1 Comparative Example 2 Comparative Example 3 Phenol / ppm 645 550 604 635 Phenylacetyl alcohol / ppm 92 54 87 88 Acetophenone / ppm 73 35 230 69 DMBA / ppm 1065 789 812 975 CHP / ppm 150 100 112 132 CM / ppm 645 895 117 552 Organic matter removal rate / % / 9.25 26.52 8.20

[0084] Table 1 shows that the removal rate of organic matter by the adsorbent is inversely proportional to the volume hourly space velocity of the material, and the removal rate can reach over 85%, especially improving the adsorption efficiency of oxygen-containing organic compounds such as phenol and phenylethanol. Furthermore, after regeneration, the organic matter removal rate is basically the same as that of fresh adsorbent, proving the feasibility of this regeneration method. Table 2 shows that after extraction, the solvent content in the aqueous phase increases, introducing new impurities and resulting in poorer treatment effects.

[0085] As described above, although the invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the invention itself. Various changes in form and detail may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims

1. An application of a solid adsorbent in the treatment of organic wastewater, characterized in that, The solid adsorbent is filled into the adsorption tower to treat organic wastewater; the organic wastewater comes from the wastewater in the production process of dicumyl peroxide; the preparation method of the solid adsorbent includes the following steps: (1) dissolving organic amine in anhydrous ethanol, stirring at 10-25°C to form a homogeneous organic amine solution; (2) adding metal ion modified porous material to the organic amine solution obtained in step (1), stirring and impregnating thoroughly at 10-25°C for 5-10 hours, filtering and drying to obtain the solid adsorbent; In step (2), the metal ion-modified porous material is prepared by the following method: (1) Weigh a soluble salt containing metals Zn, Cu or Mg, stir it in water until dissolved, and form a metal salt solution with a mass fraction of 1%-20%; (2) Take the calcined porous material and impregnate it in the metal salt solution prepared in step (1) at a temperature of 10-25℃ for 5-10h, filter and dry it to obtain the metal ion-modified porous material. The calcination refers to the removal of impurities by calcination under a N2 atmosphere, the calcination temperature is 200-400℃, and the calcination time is 6-8h; In step (2), the calcined porous material is selected from one or more of XDA-4 resin, mesoporous silica, and mesoporous alumina; the mass ratio of the porous material to the metal salt solution is 0.1-0.

25. The organic amine is selected from one or more of polyethyleneimine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethylenediamine, ethanolamine, diethanolamine, or N-methylethylene glycolamine.

2. The application according to claim 1, characterized in that, The concentration of the organic amine solution is 5%-25%, and the mass ratio of the metal ion-modified porous material to the organic amine solution is 0.01-0.

2.

3. A process for treating organic wastewater using the solid adsorbent described in claim 1, characterized in that, Organic wastewater is pumped into an adsorption tower filled with the solid adsorbent. After adsorption treatment, it enters the storage tank at the bottom of the tower and is then transported to the production unit for reuse via pipeline. The used solid adsorbent enters the adsorbent regeneration kettle, where it is regenerated by solvent desorption. The desorbed solvent enters the storage tank and is then pumped into a solvent recovery tower for treatment. The recovered solvent is obtained at the top of the tower and recycled back to the regeneration kettle for reuse, while organic matter is obtained at the bottom of the tower.

4. The process according to claim 3, characterized in that, The operating temperature inside the adsorption tower is 20-30℃, and the material volume hourly space velocity is 0.125-1 min. -1 .

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