Adsorbent for treating chemical wastewater, and preparation method

Abstract

The present invention provides an adsorbent for treating chemical wastewater, and a preparation method. The adsorbent for treating chemical wastewater comprises the following raw materials in parts by weight: 30-50 parts of activated coke, 20-30 parts of gasified pulverized coal, 25-35 parts of polyaluminium chloride, 10-20 parts of modified zeolite, 8-10 parts of [1,1'-Biphenyl]-3,4',5-tricarboxaldehyde, 10-12 parts of triphenylene-1,5,9-triamine, 0.5-1.0 part of cobalt chloride, and 3-5 parts of nonylphenol ethoxylate, wherein the modified zeolite is zeolite grafted with polyethyleneimine on its surface. The adsorbent for treating chemical wastewater can achieve good adsorption and removal effects on organic pollutants and inorganic ions such as ammonia nitrogen in wastewater.

Description

An adsorbent for treating chemical wastewater and its preparation method Technical Field

[0001] This invention relates to the field of wastewater treatment technology, and in particular to an adsorbent for treating chemical wastewater and its preparation method. Background Technology

[0002] Coking wastewater refers to the wastewater generated during coal coking, coal gas purification, chemical product recovery, and chemical product refining. Coking wastewater has a complex composition and high pollutant concentration, making it difficult to meet treatment standards. In particular, it contains organic pollutants such as polycyclic aromatic hydrocarbons (PAHs), which are difficult to degrade. Furthermore, coking wastewater also contains toxic and harmful substances such as ammonia nitrogen, with excessively high nitrogen content, leading to a nitrogen surplus required for biological purification and posing a challenge to biological treatment.

[0003] Currently, existing adsorbents are often not ideal for treating complex coking wastewater, and it is difficult to achieve good treatment results for both organic pollutants and inorganic ions such as ammonia nitrogen at the same time. Summary of the Invention

[0004] The purpose of this invention is to provide an adsorbent for treating chemical wastewater, thereby solving the problem that existing adsorbents are difficult to simultaneously treat organic pollutants and inorganic ions such as ammonia nitrogen when treating coking wastewater.

[0005] To solve the above-mentioned technical problems, the technical solution of the present invention is as follows:

[0006] An adsorbent for treating chemical wastewater comprises the following raw materials in parts by weight:

[0007] The composition includes 30-50 parts activated coke, 20-30 parts gasified coal powder, 25-35 parts polyaluminum chloride, 10-20 parts modified zeolite, 8-10 parts 3,4',5-trialdehyde-1,1-biphenyl, 10-12 parts benzo[a]phenanthrene-1,5,9-triamine, 0.5-1.0 parts cobalt chloride, and 3-5 parts nonylphenol polyoxyethylene ether; wherein the modified zeolite is a zeolite with surface grafted polyethyleneimine.

[0008] The 3,4',5-trialdehyde-1,1-biphenyl has the following structure:

[0009] The benzo[a]phenanthrene-1,5,9-triamine has the following structure:

[0010] Preferably, the gasified coal powder is a solid product obtained by gasification reaction of coal powder with oxygen-enriched gas and water vapor.

[0011] Preferably, in the gasified coal powder, the proportion of gasified coal powder with a pore size of 50 nm or more is greater than or equal to 20%.

[0012] Preferably, in the activated coke, the proportion of activated coke with a pore size in the range of 1-50 nm is 15%-30%.

[0013] It should be noted that the nonylphenol polyoxyethylene ether is a surfactant, and its CAS number is 9016-45-9.

[0014] The present invention also provides a method for preparing an adsorbent for treating chemical wastewater, comprising the following steps: taking 3,4',5-trialdehyde-1,1-biphenyl and benzo[n]phenanthrene-1,5,9-triamine, mixing them evenly, and reacting to obtain a first intermediate; mixing the first intermediate with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, modified zeolite, and nonylphenol polyoxyethylene ether evenly to obtain the final product.

[0015] Preferably, the gasified coal powder is obtained by the following method: at 1200-1350℃, coal powder is reacted with oxygen-enriched gas and water vapor to obtain a solid product;

[0016] The volume ratio of the oxygen-enriched gas to the water vapor is (16-20):1, and the oxygen content of the oxygen-enriched gas is 25-35%; in the gasification reaction, each 1 kg of pulverized coal is mixed with 0.8-1.2 m³ of steam. 3 The oxygen-rich gas undergoes a gasification reaction.

[0017] Preferably, the modified zeolite is obtained by the following method:

[0018] (1) Soak the zeolite in a hydrochloric acid solution with a concentration of 0.1-0.3 mol / L for 3-5 hours, filter, wash and dry to obtain acidified zeolite;

[0019] (2) Add 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), react at 80-100℃ for 5-8h, filter, wash and dry to obtain the coupled polymerized zeolite.

[0020] (3) Add polyethyleneimine and formaldehyde solution to the zeolite obtained in step (2) and react at 50-80℃ for 1-12 hours. Filter, wash and dry.

[0021] It should be noted that the toluene solution refers to liquid toluene.

[0022] Preferably, the modified zeolite is obtained by the following method:

[0023] (1) Add zeolite with an average particle size of 30 μm to a hydrochloric acid solution with a concentration of 0.1-0.3 mol / L and soak for 3-5 h. After filtration, washing and drying, acidified zeolite is obtained.

[0024] (2) Add 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reflux at 80-100℃ for 5-8h, filter, wash and dry to obtain the coupled polymerized zeolite.

[0025] The mass ratio of the acidified zeolite to 3-aminopropyltrimethoxysilane is 1:(0.01-0.03); the volume ratio of the acidified zeolite to the toluene solution is 1:(1.5-2.5).

[0026] (3) Add polyethyleneimine and formaldehyde solution to the zeolite obtained in step (2) and react at 50-80℃ for 1-12 hours. Filter, wash and dry.

[0027] The mass ratio of the coupled polymerized zeolite to polyethyleneimine is 1:(0.02-0.05); the mass concentration of the formaldehyde solution is 0.1-0.3%; and the volume ratio of the coupled polymerized zeolite to the formaldehyde solution is 1:(1.5-3.5).

[0028] Preferably, the method for preparing the adsorbent for treating chemical wastewater further includes the steps of grinding and passing the activated coke, gasified coal powder, and modified zeolite through a 200-325 mesh sieve.

[0029] Preferably, the first intermediate is obtained by the following method:

[0030] 3,4',5-trialdehyde-1,1-biphenyl and benzophenanthrene-1,5,9-triamine were added to tetrahydrofuran solvent, and sulfuric acid was added. The mixture was reacted at 50-80°C for 10-90 h. The crystalline precipitate was filtered and dried to obtain the first intermediate.

[0031] The molar ratio of sulfuric acid to 3,4',5-trialdehyde-1,1-biphenyl is 1:(1000-2000); the concentration of 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100-240 g / L.

[0032] Preferably, the method for preparing the adsorbent for treating chemical wastewater involves uniformly mixing the first intermediate with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, modified zeolite, and nonylphenol polyoxyethylene ether, specifically including:

[0033] The first intermediate, along with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, modified zeolite, and nonylphenol polyoxyethylene ether, is added to a tetrahydrofuran solvent and stirred for 12-24 hours. The solvent is then removed to obtain the final product.

[0034] The concentration of cobalt chloride in the tetrahydrofuran solvent is 10-20 g / L.

[0035] The above-described solution of the present invention has at least the following beneficial effects:

[0036] (1) The adsorbent for treating chemical wastewater of the present invention comprises the following raw materials in parts by weight: 30-50 parts activated coke, 20-30 parts gasified coal powder, 25-35 parts polyaluminum chloride, 10-20 parts modified zeolite, 8-10 parts 3,4',5-trialdehyde-1,1-biphenyl, 10-12 parts benzo[a]phenanthrene-1,5,9-triamine, 0.5-1.0 parts cobalt chloride, and 3-5 parts nonylphenol polyoxyethylene ether; wherein the modified zeolite is zeolite with surface grafted polyethyleneimine. The adsorbent for treating chemical wastewater can achieve good adsorption and removal effects on organic pollutants and inorganic ions such as ammonia nitrogen in the wastewater.

[0037] The activated coke has a mesoporous structure of 1-50 nm, while the gasified coal powder has a macroporous structure greater than 50 nm. Both have a large specific surface area, and their combined action can effectively adsorb organic pollutants and ammonia nitrogen molecules of different relative molecular weights. Furthermore, the addition of the gasified coal powder can prevent activated coke agglomeration. The polyaluminum chloride is an inorganic polymeric coagulant that, through the interaction of charged suspended particles, utilizes the bridging effect of hydroxide ions and the polymerization effect of polyvalent anions to produce inorganic polymers with large molecular weights and high charges. This destabilizes suspended colloids in water, causing them to aggregate into larger clusters, thereby promoting their precipitation and separation from the water.

[0038] The modified zeolite is a zeolite with polyethyleneimine grafted onto its surface. Zeolite itself has a porous structure, providing a large surface area and pore space, thus exhibiting a high adsorption capacity and effectively adsorbing ammonia nitrogen molecules through physical adsorption. Grafting polyethyleneimine onto the zeolite surface has several advantages. First, polyethyleneimine has multiple imine groups that can form hydrogen bonds with ammonia nitrogen molecules, enhancing the binding force between ammonia nitrogen molecules in wastewater and the zeolite surface, thereby improving the adsorption efficiency of ammonia nitrogen. Simultaneously, as a cationic polymer, polyethyleneimine-grafted zeolite can possess higher hydrophilicity and surface activity, forming complexes or salt precipitates with anionic substances, thereby improving the adsorption efficiency of organic matter. Second, both the activated coke and the gasified coal powder are negatively charged. With the continuous adsorption of positively charged pollutants, charge neutralization occurs, leading to increased attraction between the activated coke and gasified coal powder particles, resulting in particle agglomeration and decreased adsorption efficiency. Surface-grafted polyethyleneimine, through surface ion exchange, adsorbs or releases ions, acting as an ion buffer, reducing particle agglomeration and improving the adsorption effect.

[0039] Because the activated coke and the gasified coal powder have relatively low hydrophilicity, the hydrophobic interaction between particles will cause some particles to aggregate into clusters, reducing the contact area with water and thus reducing surface energy. The nonylphenol polyoxyethylene ether, as a surfactant, can form a structurally stable micelle structure with the activated coke and the gasified coal powder in the aqueous phase, reducing the agglomeration of the activated coke and gasified coal powder. Simultaneously, the polyoxyethylene chains in the molecular chain of the nonylphenol polyoxyethylene ether are polar groups, which can adsorb ammonia nitrogen molecules in water, bridging the intermolecular molecules. Combined with the polyaluminum chloride, it can cause the ammonia nitrogen molecules to coagulate and form large flocs, thereby accelerating the removal of ammonia nitrogen molecules through flocculation and accelerating the sedimentation of particles in the suspension.

[0040] The aldehyde group of the 3,4',5-trialdehyde-1,1-biphenyl reacts with the amino group of the benzo[a]phenanthrene-1,5,9-triamine to form a first intermediate with a cross-linked structure. This first intermediate, acting as an organic ligand, is mixed with raw materials such as cobalt chloride, activated coke, gasified coal powder, and modified zeolite. The activated coke, gasified coal powder, and modified zeolite serve as carriers. Under stirring, the first intermediate is uniformly dispersed. Simultaneously, cobalt ions in the cobalt chloride coordinate with the first intermediate to form a metal-organic cage polymer. As an ionic compound with a porous cage structure, this metal-organic cage polymer exhibits good hydrophilicity and a window radius of approximately [missing information]. It exhibits excellent selectivity for ammonia nitrogen molecules in coking wastewater. In particular, through the adsorption of the metal-organic cage polymer with the activated coke, gasified coal powder, and modified zeolite, and the flocculation and sedimentation effects of the polyaluminum chloride and nonylphenol polyoxyethylene ether, a better enrichment and removal effect of ammonia nitrogen molecules is achieved, accelerating the removal of ammonia nitrogen molecules.

[0041] (2) The adsorbent for treating chemical wastewater of the present invention comprises a modified zeolite prepared by first acidifying the zeolite, then using 3-aminopropyltrimethoxysilane to prepare a coupling polymer, and finally grafting polyethyleneimine onto it and crosslinking it with formaldehyde. This forms an inorganic-silane coupling agent-organic structure on the zeolite surface, resulting in a strong bond between the polyethyleneimine and the zeolite, extending the service life of the modified zeolite and maintaining good adsorption performance for a longer period. The amino groups introduced by the 3-aminopropyltrimethoxysilane can also increase the active sites on the zeolite surface and improve the adsorption rate. Detailed Implementation

[0042] Unless otherwise specified in the embodiments of this invention, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available products; different manufacturers and models of raw materials do not affect the implementation of the technical solution or the achievement of the technical effect of this invention.

[0043] Example 1

[0044] The adsorbent used for treating chemical wastewater in this embodiment comprises the following raw materials in parts by weight:

[0045] 30 parts activated coke, 25 parts gasified coal powder, 35 parts polyaluminum chloride, 8 parts 3,4',5-trialdehyde-1,1-biphenyl, 10 parts benzo[a]phenanthrene-1,5,9-triamine, and 0.6 parts cobalt chloride.

[0046] The gasified coal powder is a solid product obtained by gasifying coal powder with oxygen-enriched gas and water vapor. Of the gasified coal powder, 20% has a pore size of 50 nm or larger. Of the activated coke, 30% has a pore size in the range of 1-50 nm.

[0047] The method for preparing the adsorbent for treating chemical wastewater in this embodiment includes the following steps:

[0048] 3,4',5-trialdehyde-1,1-biphenyl and benzophenanthrene-1,5,9-triamine were added to tetrahydrofuran solvent, and sulfuric acid was added. The mixture was reacted at 50°C for 50 h. The crystalline precipitate was filtered and dried to obtain the first intermediate.

[0049] The molar ratio of sulfuric acid to 3,4',5-trialdehyde-1,1-biphenyl is 1:1000; the concentration of 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 180 g / L.

[0050] The first intermediate, along with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, and modified zeolite, was added to a tetrahydrofuran solvent and stirred for 12 hours. The solvent was then removed to obtain the final product.

[0051] The concentration of cobalt chloride in the tetrahydrofuran solvent is 20 g / L.

[0052] The gasified pulverized coal is obtained by the following method:

[0053] A coal gasifier is used to gasify pulverized coal with an average particle size of 60 μm with oxygen-enriched gas and water vapor at 1200℃. The pulverized coal is then held in the coal gasifier for 10 seconds to obtain a solid product.

[0054] The volume ratio of the oxygen-enriched gas to the water vapor is 18:1, and the oxygen-enriched gas is oxygen-enriched air with an oxygen content of 25%; in the gasification reaction, every 1 kg of pulverized coal is mixed with 1.0 m³ of water vapor. 3 The oxygen-rich gas undergoes a gasification reaction.

[0055] Example 2

[0056] The adsorbent used for treating chemical wastewater in this embodiment comprises the following raw materials in parts by weight:

[0057] 40 parts activated coke, 20 parts gasified coal powder, 25 parts polyaluminum chloride, 9 parts 3,4',5-trialdehyde-1,1-biphenyl, 12 parts benzo[a]phenanthrene-1,5,9-triamine, and 0.5 parts cobalt chloride.

[0058] The gasified coal powder is a solid product obtained by gasifying coal powder with oxygen-enriched gas and water vapor. Of the gasified coal powder, 25% has a pore size of 50 nm or larger. Of the activated coke, 15% has a pore size in the range of 1-50 nm.

[0059] The method for preparing the adsorbent for treating chemical wastewater in this embodiment includes the following steps:

[0060] 3,4',5-trialdehyde-1,1-biphenyl and benzophenanthrene-1,5,9-triamine were added to tetrahydrofuran solvent, and sulfuric acid was added. The mixture was reacted at 80°C for 90 h. The crystalline precipitate was filtered and dried to obtain the first intermediate.

[0061] The molar ratio of sulfuric acid to 3,4',5-trialdehyde-1,1-biphenyl is 1:2000; the concentration of 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 240 g / L.

[0062] The first intermediate, along with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, and modified zeolite, was added to a tetrahydrofuran solvent and stirred for 20 hours. The solvent was then removed to obtain the final product.

[0063] The concentration of cobalt chloride in the tetrahydrofuran solvent is 15 g / L.

[0064] The gasified pulverized coal is obtained by the following method:

[0065] A coal gasifier is used to gasify pulverized coal with an average particle size of 60 μm at 1250 °C with oxygen-enriched gas and water vapor, and the pulverized coal is kept in the coal gasifier for 20 s to obtain a solid product.

[0066] The volume ratio of the oxygen-enriched gas to the water vapor is 20:1, and the oxygen-enriched gas is oxygen-enriched air with an oxygen content of 35%; in the gasification reaction, every 1 kg of pulverized coal is mixed with 1.2 m³ of water vapor. 3 The oxygen-rich gas undergoes a gasification reaction.

[0067] Example 3

[0068] The adsorbent used for treating chemical wastewater in this embodiment comprises the following raw materials in parts by weight:

[0069] 50 parts activated coke, 30 parts gasified coal powder, 30 parts polyaluminum chloride, 10 parts 3,4',5-trialdehyde-1,1-biphenyl, 11 parts benzo[a]phenanthrene-1,5,9-triamine, and 1.0 part cobalt chloride.

[0070] The gasified coal powder is a solid product obtained by gasifying coal powder with oxygen-enriched gas and water vapor. Of the gasified coal powder, 35% has a pore size of 50 nm or larger. Of the activated coke, 27% has a pore size in the range of 1-50 nm.

[0071] The method for preparing the adsorbent for treating chemical wastewater in this embodiment includes the following steps:

[0072] 3,4',5-trialdehyde-1,1-biphenyl and benzophenanthrene-1,5,9-triamine were added to tetrahydrofuran solvent, and sulfuric acid was added. The mixture was reacted at 60°C for 10 h. The crystalline precipitate was filtered and dried to obtain the first intermediate.

[0073] The molar ratio of sulfuric acid to 3,4',5-trialdehyde-1,1-biphenyl is 1:1500; the concentration of 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100 g / L.

[0074] The first intermediate, along with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, and modified zeolite, was added to a tetrahydrofuran solvent and stirred for 24 hours. The solvent was then removed to obtain the final product.

[0075] The concentration of cobalt chloride in the tetrahydrofuran solvent is 10 g / L.

[0076] The gasified pulverized coal is obtained by the following method:

[0077] A coal gasifier is used to gasify pulverized coal with an average particle size of 60 μm with oxygen-enriched gas and water vapor at 1350℃. The pulverized coal is then held in the coal gasifier for 15 seconds to obtain a solid product.

[0078] The volume ratio of the oxygen-enriched gas to the water vapor is 16:1, and the oxygen-enriched gas is oxygen-enriched air with an oxygen content of 30%. In the gasification reaction, each 1 kg of pulverized coal is mixed with 0.8 m³ of water vapor. 3 The oxygen-rich gas undergoes a gasification reaction.

[0079] Example 4

[0080] The adsorbent for treating chemical wastewater in this embodiment comprises the following raw materials in parts by weight:

[0081] 35 parts activated coke, 28 parts gasified coal powder, 30 parts polyaluminum chloride, 15 parts modified zeolite, 9 parts 3,4',5-trialdehyde-1,1-biphenyl, 12 parts benzo[a]phenanthrene-1,5,9-triamine, and 0.8 parts cobalt chloride.

[0082] The gasified coal powder is a solid product obtained by gasifying coal powder with oxygen-enriched gas and water vapor. Of the gasified coal powder, 35% has a pore size of 50 nm or larger. Of the activated coke, 30% has a pore size in the range of 1-50 nm. The modified zeolite is a zeolite with surface grafted polyethyleneimine.

[0083] The method for preparing the adsorbent for treating chemical wastewater in this embodiment includes the following steps:

[0084] 3,4',5-trialdehyde-1,1-biphenyl and benzophenanthrene-1,5,9-triamine were added to tetrahydrofuran solvent, and sulfuric acid was added. The mixture was reacted at 80°C for 60 h. The crystalline precipitate was filtered and dried to obtain the first intermediate.

[0085] The molar ratio of sulfuric acid to 3,4',5-trialdehyde-1,1-biphenyl is 1:1800; the concentration of 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 200 g / L.

[0086] The first intermediate, along with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, and modified zeolite, was added to a tetrahydrofuran solvent and stirred for 24 hours. The solvent was then removed to obtain the final product.

[0087] The concentration of cobalt chloride in the tetrahydrofuran solvent is 20 g / L.

[0088] The gasified pulverized coal is obtained by the following method:

[0089] A coal gasifier is used to gasify pulverized coal with an average particle size of 60 μm with oxygen-enriched gas and water vapor at 1300℃. The pulverized coal is then held in the coal gasifier for 20 seconds to obtain a solid product.

[0090] The volume ratio of the oxygen-enriched gas to the water vapor is 18:1, and the oxygen-enriched gas is oxygen-enriched air with an oxygen content of 30%. In the gasification reaction, each 1 kg of pulverized coal is mixed with 1.2 m³ of water vapor. 3 The oxygen-rich gas undergoes a gasification reaction.

[0091] The modified zeolite is obtained by the following method:

[0092] (1) Zeolite with an average particle size of 30 μm was soaked in a 0.2 mol / L hydrochloric acid solution for 5 h, filtered, washed and dried to obtain acidified zeolite;

[0093] (2) Add 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reflux at 80°C for 6 hours, filter, wash and dry to obtain the coupled polymerized zeolite.

[0094] The mass ratio of the acidified zeolite to 3-aminopropyltrimethoxysilane is 1:0.02; the volume ratio of the acidified zeolite to the toluene solution is 1:2.

[0095] (3) Add polyethyleneimine and formaldehyde solution to the zeolite obtained in step (2) and react at 60°C for 5 hours. Filter, wash and dry to obtain the final product.

[0096] The mass ratio of the coupled polymerized zeolite to polyethyleneimine is 1:0.03; the mass concentration of the formaldehyde solution is 0.1%; and the volume ratio of the coupled polymerized zeolite to the formaldehyde solution is 1:1.8.

[0097] Example 5

[0098] The adsorbent for treating chemical wastewater in this embodiment comprises the following raw materials in parts by weight:

[0099] 35 parts activated coke, 28 parts gasified coal powder, 30 parts polyaluminum chloride, 10 parts modified zeolite, 12 parts 3,4',5-trialdehyde-1,1-biphenyl, 12 parts benzo[a]phenanthrene-1,5,9-triamine, and 1.0 part cobalt chloride.

[0100] The gasified coal powder is a solid product obtained by gasifying coal powder with oxygen-enriched gas and water vapor. Of the gasified coal powder, 35% has a pore size of 50 nm or larger. Of the activated coke, 30% has a pore size in the range of 1-50 nm. The modified zeolite is a zeolite with surface grafted polyethyleneimine.

[0101] The method for preparing the adsorbent for treating chemical wastewater in this embodiment includes the following steps:

[0102] 3,4',5-trialdehyde-1,1-biphenyl and benzophenanthrene-1,5,9-triamine were added to tetrahydrofuran solvent, and sulfuric acid was added. The mixture was reacted at 60°C for 10 h. The crystalline precipitate was filtered and dried to obtain the first intermediate.

[0103] The molar ratio of sulfuric acid to 3,4',5-trialdehyde-1,1-biphenyl is 1:1000; the concentration of 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100 g / L.

[0104] Take activated coke, gasified coal powder, and modified zeolite, grind them, and pass them through a 325-mesh sieve. Add the first intermediate, cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, and modified zeolite into a tetrahydrofuran solvent, stir for 24 hours, remove the solvent, and you will get the product.

[0105] The concentration of cobalt chloride in the tetrahydrofuran solvent is 10 g / L.

[0106] The gasified pulverized coal is obtained by the following method:

[0107] A coal gasifier is used to gasify pulverized coal with an average particle size of 60 μm with oxygen-enriched gas and water vapor at 1300℃. The pulverized coal is then held in the coal gasifier for 20 seconds to obtain a solid product.

[0108] The volume ratio of the oxygen-enriched gas to the water vapor is 18:1, and the oxygen-enriched gas is oxygen-enriched air with an oxygen content of 30%. In the gasification reaction, each 1 kg of pulverized coal is mixed with 1.2 m³ of water vapor. 3 The oxygen-rich gas undergoes a gasification reaction.

[0109] The modified zeolite is obtained by the following method:

[0110] (1) Zeolite with an average particle size of 30 μm was soaked in a 0.2 mol / L hydrochloric acid solution for 5 h, filtered, washed and dried to obtain acidified zeolite;

[0111] (2) Add 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reflux at 90°C for 5 h, filter, wash and dry to obtain the coupled polymerized zeolite.

[0112] The mass ratio of the acidified zeolite to 3-aminopropyltrimethoxysilane is 1:0.01; the volume ratio of the acidified zeolite to the toluene solution is 1:1.5.

[0113] (3) Add polyethyleneimine and formaldehyde solution to the zeolite obtained in step (2) and react at 80°C for 1 hour. Filter, wash and dry.

[0114] The mass ratio of the coupled polymerized zeolite to polyethyleneimine is 1:0.05; the mass concentration of the formaldehyde solution is 0.3%; and the volume ratio of the coupled polymerized zeolite to the formaldehyde solution is 1:3.5.

[0115] Example 6

[0116] The adsorbent for treating chemical wastewater in this embodiment comprises the following raw materials in parts by weight:

[0117] 35 parts activated coke, 28 parts gasified coal powder, 30 parts polyaluminum chloride, 20 parts modified zeolite, 9 parts 3,4',5-trialdehyde-1,1-biphenyl, 8 parts benzo[a]phenanthrene-1,5,9-triamine, and 0.5 parts cobalt chloride.

[0118] The gasified coal powder is a solid product obtained by gasifying coal powder with oxygen-enriched gas and water vapor. Of the gasified coal powder, 35% has a pore size of 50 nm or larger. Of the activated coke, 30% has a pore size in the range of 1-50 nm. The modified zeolite is a zeolite with surface grafted polyethyleneimine.

[0119] The method for preparing the adsorbent for treating chemical wastewater in this embodiment includes the following steps:

[0120] 3,4',5-trialdehyde-1,1-biphenyl and benzophenanthrene-1,5,9-triamine were added to tetrahydrofuran solvent, and sulfuric acid was added. The mixture was reacted at 80°C for 90 h. The crystalline precipitate was filtered and dried to obtain the first intermediate.

[0121] The molar ratio of sulfuric acid to 3,4',5-trialdehyde-1,1-biphenyl is 1:2000; the concentration of 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 240 g / L.

[0122] The first intermediate, along with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, modified zeolite, and tetrahydrofuran solvent, was added and stirred for 24 hours. The solvent was then removed to obtain the final product.

[0123] The concentration of cobalt chloride in the tetrahydrofuran solvent is 20 g / L.

[0124] The gasified pulverized coal is obtained by the following method:

[0125] A coal gasifier is used to gasify pulverized coal with an average particle size of 60 μm with oxygen-enriched gas and water vapor at 1300℃. The pulverized coal is then held in the coal gasifier for 20 seconds to obtain a solid product.

[0126] The volume ratio of the oxygen-enriched gas to the water vapor is 18:1, and the oxygen-enriched gas is oxygen-enriched air with an oxygen content of 30%. In the gasification reaction, each 1 kg of pulverized coal is mixed with 1.2 m³ of water vapor. 3 The oxygen-rich gas undergoes a gasification reaction.

[0127] The modified zeolite is obtained by the following method:

[0128] (1) Zeolite with an average particle size of 30 μm was soaked in a 0.2 mol / L hydrochloric acid solution for 5 h, filtered, washed and dried to obtain acidified zeolite;

[0129] (2) Add 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reflux at 100°C for 8 hours, filter, wash and dry to obtain the coupled polymerized zeolite.

[0130] The mass ratio of the acidified zeolite to 3-aminopropyltrimethoxysilane is 1:0.03; the volume ratio of the acidified zeolite to the toluene solution is 1:2.5.

[0131] (3) Add polyethyleneimine and formaldehyde solution to the zeolite obtained in step (2) and react at 50°C for 12 hours. Filter, wash and dry to obtain the final product.

[0132] The mass ratio of the coupled polymerized zeolite to polyethyleneimine is 1:0.02; the mass concentration of the formaldehyde solution is 0.2%; and the volume ratio of the coupled polymerized zeolite to the formaldehyde solution is 1:1.5.

[0133] Example 7

[0134] This comparative example uses the same adsorbent as Example 4 for treating chemical wastewater, except that it also includes 4 parts by weight of nonylphenol polyoxyethylene ether.

[0135] The preparation method of the adsorbent for treating chemical wastewater in this embodiment is the same as that in Example 4, except that it also includes the step of adding nonylphenol polyoxyethylene ether, as detailed below:

[0136] Take 3,4',5-trialdehyde-1,1-biphenyl and benzo[a]phenanthrene-1,5,9-triamine, mix them evenly, and react to obtain the first intermediate; mix the first intermediate with cobalt chloride, activated coke, gasified coal powder, polyaluminum chloride, modified zeolite, and nonylphenol polyoxyethylene ether evenly to obtain the final product.

[0137] Comparative Example 1

[0138] This comparative example uses the same adsorbent for treating chemical wastewater as in Example 4, and was prepared using the same method, except that it does not contain gasified coal powder.

[0139] Comparative Example 2

[0140] This comparative example uses the same adsorbent for treating chemical wastewater as in Example 4, and was prepared using the same method, except that the modified zeolite was replaced with unmodified zeolite.

[0141] Comparative Example 3

[0142] This comparative example uses the same adsorbent for treating chemical wastewater as in Example 4, and was prepared using the same method. The only difference is that the modified zeolite was prepared differently.

[0143] In step (2) of the modified zeolite preparation method in this comparative example, the mass ratio of the acidified zeolite to 3-aminopropyltrimethoxysilane is 1:0.05. In step (3), the mass ratio of the coupling polymerized zeolite to polyethyleneimine is 1:0.08.

[0144] Comparative Example 4

[0145] This comparative example uses the same adsorbent for treating chemical wastewater as in Example 4, and was prepared using the same method. The only difference is that the modified zeolite was prepared differently.

[0146] In step (2) of the modified zeolite preparation method in this comparative example, the mass ratio of the acidified zeolite to 3-aminopropyltrimethoxysilane is 1:0.01. In step (3), the mass ratio of the coupling polymerized zeolite to polyethyleneimine is 1:0.01.

[0147] Comparative Example 5

[0148] This comparative example uses the same adsorbent for treating chemical wastewater as Example 4, and was prepared using the same method. The only difference is that the preparation method of the modified zeolite is different, as detailed below:

[0149] (1) Zeolite with an average particle size of 30 μm was soaked in a 0.2 mol / L hydrochloric acid solution for 5 h, filtered, washed and dried to obtain acidified zeolite;

[0150] (2) Add polyethyleneimine and formaldehyde solution to the acidified zeolite obtained in step (1), react at 60°C for 5 hours, filter, wash and dry.

[0151] The mass ratio of the acidified zeolite to polyethyleneimine is 1:0.03; the mass concentration of the formaldehyde solution is 0.1%; and the volume ratio of the coupled polymerized zeolite to the formaldehyde solution is 1:1.8.

[0152] Comparative Example 6

[0153] This comparative example uses the same adsorbent for treating chemical wastewater as in Example 4, and was prepared using the same method, except that it does not contain the modified zeolite.

[0154] Comparative Example 7

[0155] This comparative example uses the same adsorbent for treating chemical wastewater as in Example 7, and was prepared using the same method, except that it does not contain the polyaluminum chloride.

[0156] Comparative Example 8

[0157] This comparative example uses the same adsorbent for treating chemical wastewater as in Example 7, and was prepared using the same method. The only difference is that it does not contain the 3,4',5-trialdehyde-1,1-biphenyl and benzo[a]phenanthrene-1,5,9-triamine.

[0158] Effect Experiment Example

[0159] To verify the technical effectiveness of the adsorbent for treating chemical wastewater described in this invention, the following experiments were conducted:

[0160] Take the coking wastewater to be treated and measure its COD concentration to be 162 mg / L and ammonia nitrogen concentration to be 236 mg / L. Then take 10 g of the adsorbent prepared in Examples 1-7 and Comparative Examples 1-8 for treating chemical wastewater as samples and add it to 800 ml of coking wastewater. Stir continuously and measure the COD concentration and ammonia nitrogen concentration after treatment after 30 min and 6 h, respectively. Calculate the COD removal rate and ammonia nitrogen removal rate.

[0161] The results of the experiment are as follows:

[0162] Based on the above experimental results, it can be seen that the adsorbent for treating chemical wastewater described in this invention can achieve good adsorption and removal effects on organic pollutants and inorganic ions such as ammonia nitrogen in wastewater.

[0163] Based on the results of Examples 1-3, Examples 4-6, and Comparative Example 6, it is evident that the addition of the modified zeolite improved the COD and ammonia nitrogen removal rates. Based on the results of Example 4 and Comparative Example 1, it is evident that the addition of the gasified coal powder significantly improved the COD and ammonia nitrogen removal rates. Based on the results of Examples 1-4 and Comparative Example 2, it is evident that the unmodified zeolite did not significantly improve the COD and ammonia nitrogen removal rates.

[0164] Based on the results of Example 4 and Comparative Example 5, it can be seen that although the COD removal rate and ammonia nitrogen removal rate of the modified zeolite without coupling with the 3-aminopropyltrimethoxysilane were not significantly different from those of Example 4 after 30 minutes of treatment, the COD removal rate and ammonia nitrogen removal rate were significantly reduced after 6 hours of treatment, indicating a significant performance decline. Based on the results of Example 4 and Comparative Examples 3-4, it can be seen that the amount of 3-aminopropyltrimethoxysilane and polyethyleneimine used in the preparation of the modified zeolite has a significant impact on the adsorbent effect. In other words, the grafting rate of the modified zeolite has a significant impact on the adsorbent effect. When the grafting rate is too low, the improvement effect on COD removal rate and ammonia nitrogen removal rate is not significant; when the grafting rate is too high, the COD removal rate and ammonia nitrogen removal rate actually decrease to some extent.

[0165] Based on the results of Examples 4 and 7 and Comparative Example 7, it is evident that the addition of polyaluminum chloride significantly improves both the removal rate and speed of COD and ammonia nitrogen molecules. The addition of nonylphenol polyoxyethylene ether greatly enhances the ammonia nitrogen removal rate after 30 minutes of adsorbent treatment, and also slightly increases the COD removal rate after 30 minutes, accelerating the removal of ammonia nitrogen molecules and organic pollutants, especially ammonia nitrogen molecules. The synergistic use of both significantly improves the overall adsorption effect.

[0166] Based on the results of Example 7 and Comparative Example 8, it is evident that the addition of 3,4',5-trialdehyde-1,1-biphenyl and benzo[a]phenanthrene-1,5,9-triamine has a significant impact on the removal rate of ammonia nitrogen molecules, but a weaker impact on the COD removal rate. Therefore, the metal-organic cage polymer formed by the 3,4',5-trialdehyde-1,1-biphenyl, benzo[a]phenanthrene-1,5,9-triamine, and cobalt chloride exhibits selectivity for ammonia nitrogen molecules and a significant enhancing effect on ammonia nitrogen molecule removal.

[0167] Therefore, the adsorbent for treating chemical wastewater described in this invention, which utilizes activated coke, gasified coal powder, polyaluminum chloride, modified zeolite, 3,4',5-trialdehyde-1,1-biphenyl, benzo[a]phenanthrene-1,5,9-triamine, cobalt chloride, and nonylphenol polyoxyethylene ether, can synergistically exert adsorption effects, effectively removing organic pollutants and ammonia nitrogen inorganic ions from complex coking wastewater.

[0168] As is known from common technical knowledge, this invention can be implemented through other embodiments that do not depart from its spirit or essential characteristics. Therefore, the disclosed embodiments described above are merely illustrative in all respects and are not the only ones. All modifications within the scope of this invention or its equivalents are encompassed by this invention.

Claims

1. An adsorbent for treating chemical wastewater, characterized by comprising a porous material having a specific surface area of 500 m2 / g or more and a pore volume of 0.5 ml / g or more. The raw materials include the following weight parts: active coke 30-50 parts, gasified coal powder 20-30 parts, polyaluminum chloride 25-35 parts, modified zeolite 10-20 parts, 3,4',5-trialdehyde-1,1-biphenyl 8-10 parts, benzenophenyl-1,5,9-triamine 10-12 parts, cobalt chloride 0.5-1.0 parts, nonylphenol polyoxyethylene ether 3-5 parts; The modified zeolite is a zeolite grafted with polyethyleneimine on the surface.

2. The adsorbent for treating chemical industrial wastewater according to claim 1, characterized by, The gasified coal powder is a solid product obtained by gasification reaction of coal powder, oxygen-rich gas and water vapor.

3. The adsorbent for treating chemical industrial wastewater according to claim 2, characterized by, In the gasified coal powder, the proportion of gasified coal powder with a pore size of 50 nm or more is greater than or equal to 20%.

4. The adsorbent for treating chemical industrial wastewater according to claim 3, characterized by, In the active coke, the proportion of active coke with a pore size in the range of 1-50 nm is 15%-30%.

5. A method for preparing an adsorbent for treating chemical wastewater, characterized by, The method comprises the following steps: 3,4',5-trialdehyde-1,1-biphenyl and benzenophenyl-1,5,9-triamine are mixed uniformly to obtain a first intermediate; the first intermediate is mixed uniformly with cobalt chloride, active coke, gasified coal powder, polyaluminum chloride, modified zeolite and nonylphenol polyoxyethylene ether to obtain the product.

6. The method for preparing an adsorbent for treating chemical wastewater according to claim 5, characterized by, The gasified coal powder is obtained by gasification reaction of coal powder, oxygen-rich gas and water vapor at 1200-1350℃ to obtain a solid product; The volume ratio of the oxygen-rich gas to the water vapor is (16-20):1, and the oxygen content of the oxygen-rich gas is 25-35%; in the gasification reaction, 0.8-1.2 m 3 of the oxygen-rich gas is used for 1 kg of the coal powder.

7. The method for preparing an adsorbent for treating chemical wastewater according to claim 5, characterized by, The modified zeolite is obtained by the following method: (1) The zeolite is soaked in a hydrochloric acid solution with a concentration of 0.1-0.3 mol / L for 3-5 h, filtered, washed and dried to obtain acidified zeolite; (2) 3-aminopropyltrimethoxysilane and toluene solution are added to the acidified zeolite obtained in step (1), and the mixture is reacted at 80-100℃ for 5-8 h, filtered, washed and dried to obtain coupled and polymerized zeolite; (3) Polyethyleneimine and formaldehyde solution are added to the coupled and polymerized zeolite obtained in step (2), and the mixture is reacted at 50-80℃ for 1-12 h, filtered, washed and dried.

8. The method for preparing an adsorbent for treating chemical wastewater according to claim 7, characterized by, The method further comprises the step of grinding the active coke, gasified coal powder and modified zeolite and passing them through a 200-325 mesh sieve.

9. The method for preparing an adsorbent for treating chemical wastewater according to claim 5, characterized by, The first intermediate is obtained by the following method: 3,4',5-trialdehyde-1,1-biphenyl and benzenophenyl-1,5,9-triamine are added to a tetrahydrofuran solvent, and sulfuric acid is added, and the mixture is reacted at 50-80℃ for 10-90 h, and the crystalline precipitate is filtered and dried to obtain the first intermediate; The molar ratio of sulfuric acid to 3,4',5-trialdehyde-1,1-biphenyl is 1:(1000-2000); the concentration of 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100-240 g / L.

10. The method for preparing an adsorbent for treating chemical wastewater according to claim 9, characterized by, The first intermediate is mixed uniformly with cobalt chloride, active coke, gasified coal powder, polyaluminum chloride, modified zeolite and nonylphenol polyoxyethylene ether, specifically including: The first intermediate is mixed uniformly with cobalt chloride, active coke, gasified coal powder, polyaluminum chloride, modified zeolite and nonylphenol polyoxyethylene ether, specifically including: The concentration of cobalt chloride in the tetrahydrofuran solvent is 10-20 g / L.

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