A kind of adsorbent for treating chemical wastewater and preparation method thereof

Abstract

The present invention provides an adsorbent for treating chemical wastewater and a preparation method thereof, wherein 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 coal powder, 25-35 parts of polyaluminium chloride, 10-20 parts of modified zeolite, 8-10 parts of 3,4',5-trialdehyde-1,1-biphenyl, 10-12 parts of triphenylene-1,5,9-triamine, 0.5-1.0 parts of cobalt chloride, and 3-5 parts of nonylphenol polyoxyethylene ether; wherein the modified zeolite is a zeolite with polyethyleneimine grafted on the surface. The adsorbent for treating chemical wastewater can achieve good adsorption and removal effects on organic pollutants and ammonia nitrogen inorganic ions in wastewater.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, in particular to an adsorbent for treating chemical wastewater and a preparation method thereof. Background Art

[0002] Coking wastewater refers to wastewater generated during coal coking, coal gas purification, chemical product recovery and chemical product refining. The composition of coking wastewater is complex, the concentration of pollutants is high, and it is difficult to treat it in compliance with standards. In particular, coking wastewater contains organic pollutants such as polycyclic aromatic hydrocarbons, which are difficult to degrade. In addition, coking wastewater also contains toxic and harmful substances such as ammonia nitrogen. Its nitrogen content is too high, resulting in an excess of nitrogen sources required for biological purification, which also brings difficulties to biological treatment.

[0003] At present, when treating coking wastewater with complex components, the existing adsorbents are often not ideal and it is difficult to achieve good treatment effects on both organic pollutants and ammonia nitrogen inorganic ions at the same time. Summary of the invention

[0004] The purpose of the present invention is to provide an adsorbent for treating chemical wastewater, so as to solve the problem that it is difficult to take into account the treatment effects of organic pollutants and ammonia nitrogen inorganic ions when treating coking wastewater with adsorbents in the prior art.

[0005] In order to solve the above technical problems, the technical solution of the present invention is as follows:

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

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

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

[0009]

[0010] The triphenylene-1,5,9-triamine has the following structure:

[0011]

[0012] Preferably, the gasified coal powder is a solid product obtained by gasification reaction of coal powder, oxygen-rich gas and water vapor.

[0013] 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%.

[0014] Preferably, among the activated coke, the active coke with a pore size in the range of 1-50 nm accounts for 15%-30%.

[0015] It should be noted that the nonylphenol polyoxyethylene ether is a surfactant, and its CAS number is 9016-45-9.

[0016] 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 triphenylene-1,5,9-triamine, mixing them evenly, and reacting to obtain a first intermediate; and evenly mixing the first intermediate with cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride, modified zeolite and nonylphenol polyoxyethylene ether to obtain the adsorbent.

[0017] Preferably, the gasified coal powder is obtained by the following method: at 1200-1350° C., the coal powder is subjected to a gasification reaction with oxygen-rich gas and water vapor to obtain a solid product;

[0018] 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, 1 kg of coal powder is mixed with 0.8-1.2 m 3 The oxygen-rich gas is subjected to a gasification reaction.

[0019] Preferably, the modified zeolite is obtained by the following method:

[0020] (1) adding zeolite to a hydrochloric acid solution with a concentration of 0.1-0.3 mol / L and soaking it for 3-5 hours, filtering, washing and drying to obtain acidified zeolite;

[0021] (2) adding 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reacting at 80-100° C. for 5-8 hours, filtering, washing and drying to obtain a coupled polymerized zeolite;

[0022] (3) Add polyethyleneimine and formaldehyde solution to the coupled polymerized zeolite obtained in step (2), react at 50-80° C. for 1-12 h, filter, wash and dry.

[0023] It should be noted that the toluene solution refers to liquid toluene.

[0024] Preferably, the modified zeolite is obtained by the following method:

[0025] (1) adding zeolite with an average particle size of 30 μm into a hydrochloric acid solution with a concentration of 0.1-0.3 mol / L and soaking for 3-5 hours, filtering, washing and drying to obtain acidified zeolite;

[0026] (2) adding 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reflux reacting at 80-100° C. for 5-8 hours, filtering, washing and drying to obtain a coupled polymerized zeolite;

[0027] Wherein, 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).

[0028] (3) Add polyethyleneimine and formaldehyde solution to the coupled polymerized zeolite obtained in step (2), react at 50-80° C. for 1-12 h, filter, wash and dry.

[0029] 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).

[0030] Preferably, the method for preparing the adsorbent for treating chemical wastewater further comprises the steps of grinding the activated coke, gasified coal powder and modified zeolite and passing through a 200-325 mesh sieve.

[0031] Preferably, the first intermediate is obtained by the following method:

[0032] Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 50-80° C. for 10-90 hours, filter and dry the crystalline precipitate to obtain the first intermediate;

[0033] The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:(1000-2000); the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100-240 g / L.

[0034] Preferably, the preparation method of the adsorbent for treating chemical wastewater comprises uniformly mixing the first intermediate with cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride, modified zeolite and nonylphenol polyoxyethylene ether, and specifically comprising:

[0035] The first intermediate, cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride, modified zeolite and nonylphenol polyoxyethylene ether are added into tetrahydrofuran solvent, stirred for 12-24 hours, and the solvent is removed to obtain the product.

[0036] Wherein, the concentration of the cobalt chloride in the tetrahydrofuran solvent is 10-20 g / L.

[0037] The above solution of the present invention includes at least the following beneficial effects:

[0038] (1) The adsorbent for treating chemical wastewater of the present invention comprises the following raw materials in parts by weight: 30-50 parts of activated coke, 20-30 parts of gasified coal powder, 25-35 parts of polyaluminium chloride, 10-20 parts of modified zeolite, 8-10 parts of 3,4',5-trialdehyde-1,1-biphenyl, 10-12 parts of triphenylene-1,5,9-triamine, 0.5-1.0 parts of cobalt chloride, and 3-5 parts of nonylphenol polyoxyethylene ether; wherein the modified zeolite is a zeolite with polyethyleneimine grafted on the 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.

[0039] The activated coke has a mesoporous structure of 1-50nm, while the gasified coal powder has a macroporous structure greater than 50nm. Both have a large specific surface area, and the two cooperate with each other to effectively adsorb organic pollutants and ammonia nitrogen molecules of different relative molecular weights. In addition, the addition of the gasified coal powder can also prevent the activated coke from agglomerating. The polyaluminium chloride is an inorganic polymer coagulant. Through the interaction with charged suspended particles, the inorganic polymer with a large molecular weight and a high charge is produced by the bridging effect of hydroxide ions and the polymerization effect of multivalent anions, which destabilizes the suspended colloids in the water and aggregates them into larger clusters, thereby promoting their precipitation and separation from the water body.

[0040] The modified zeolite is a zeolite with polyethyleneimine grafted on the surface. Zeolite itself has a porous structure, which can provide a large amount of surface area and pore space, and thus has a large adsorption capacity, and can effectively adsorb ammonia nitrogen molecules by physical adsorption. Polyethyleneimine is grafted on the surface of zeolite. On the one hand, polyethyleneimine has multiple imine groups, which can form hydrogen bonds with ammonia nitrogen molecules, enhance the binding force between ammonia nitrogen molecules in wastewater and the zeolite surface, thereby improving the adsorption efficiency of ammonia nitrogen. At the same time, polyethyleneimine is a cationic polymer, and the zeolite with polyethyleneimine grafted on the surface can have higher hydrophilicity and surface activity, and form complexes or salt precipitations with anionic substances, thereby improving the adsorption efficiency of organic matter. On the other hand, the charge properties of the activated coke and the gasified coal powder are both negatively charged. With the continuous adsorption of positively charged pollutants, charge neutralization will occur, resulting in an increase in the attraction between the particles of the activated coke and the gasified coal powder, thereby causing particle agglomeration and a decrease in adsorption effect, and the surface grafted polyethyleneimine can adsorb or release ions through the surface ion exchange effect, play an ion buffering role, reduce particle agglomeration, and improve adsorption effect.

[0041] Since the hydrophilicity of the activated coke and the gasified coal powder is relatively weak, the hydrophobic effect between the particles will cause some particles to aggregate into agglomerates to reduce the contact area with water, thereby reducing the surface energy. The nonylphenol polyoxyethylene ether, as a surfactant, can form a stable micellar structure with the activated coke and the gasified coal powder in the water phase, reducing the aggregation of the activated coke and the gasified coal powder. At the same time, the polyoxyethylene chain contained in the molecular chain of the nonylphenol polyoxyethylene ether is a polar group, which can bridge between molecules by adsorbing ammonia nitrogen molecules in water, and cooperate with the polyaluminium chloride to form large floccules, thereby accelerating the removal of ammonia nitrogen molecules through flocculation and accelerating the sedimentation of particles in the suspension.

[0042] After the aldehyde group of the 3,4',5-trialdehyde-1,1-biphenyl reacts with the amino group of the triphenylene-1,5,9-triamine, a first intermediate with a cross-linked structure is formed. After the first intermediate is mixed with raw materials such as cobalt chloride, activated coke, gasified coal powder, and modified zeolite as an organic ligand, the activated coke, gasified coal powder, and modified zeolite are used as carriers to disperse the first intermediate evenly under stirring. At the same time, the cobalt ions in the cobalt chloride and the first intermediate form a metal-organic cage polymer through coordination self-assembly. As an ionic compound with a porous cage structure, the metal-organic cage polymer has good hydrophilicity, and the window radius is about 1.50-1.61Å, which has good selectivity for ammonia nitrogen molecules in coking wastewater. In particular, through the adsorption of the metal-organic cage polymer and the activated coke, gasified coal powder, and modified zeolite, the polyaluminum chloride and nonylphenol polyoxyethylene ether flocculation and sedimentation are coordinated to achieve a better enrichment and removal of ammonia nitrogen molecules, and accelerate the removal of ammonia nitrogen molecules.

[0043] (2) The adsorbent for treating chemical wastewater of the present invention, the modified zeolite is first acidified by zeolite, then a coupling polymer is prepared with 3-aminopropyltrimethoxysilane, and finally polyethyleneimine is grafted and cross-linked with formaldehyde to form an inorganic-silane coupling agent-organic structure on the surface of the zeolite, so that the polyethyleneimine and the zeolite have a good strength bond, the service life of the modified zeolite is extended, and a good adsorption effect is maintained for a longer period of time. The amino group introduced by the 3-aminopropyltrimethoxysilane can also increase the active sites on the surface of the zeolite and improve the adsorption rate. DETAILED DESCRIPTION

[0044] In the embodiments of the present invention, if the specific conditions are not specified, the conventional conditions or the conditions recommended by the manufacturer are followed. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially. Raw materials of different manufacturers and models do not affect the implementation of the technical solution of the present invention and the realization of the technical effects.

[0045] Example 1

[0046] The adsorbent for treating chemical wastewater in this embodiment includes the following raw materials in parts by weight:

[0047] 30 parts of activated coke, 25 parts of gasified coal powder, 35 parts of polyaluminium chloride, 8 parts of 3,4',5-trialdehyde-1,1-biphenyl, 10 parts of triphenylene-1,5,9-triamine, and 0.6 parts of cobalt chloride.

[0048] The gasified coal powder is a solid product obtained by gasification reaction of coal powder with oxygen-rich gas and water vapor. Among the gasified coal powder, the gasified coal powder with a pore size of 50nm or more accounts for 20%. Among the activated coke, the activated coke with a pore size of 1-50nm accounts for 30%.

[0049] The preparation method of the adsorbent for treating chemical wastewater in this embodiment comprises the following steps:

[0050] Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 50° C. for 50 hours, filter and dry the crystalline precipitate to obtain the first intermediate;

[0051] The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:1000; and the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 180 g / L.

[0052] The first intermediate, cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride and modified zeolite are added into tetrahydrofuran solvent, stirred for 12 hours, and the solvent is removed to obtain;

[0053] Wherein, the concentration of the cobalt chloride in the tetrahydrofuran solvent is 20 g / L.

[0054] The gasified coal powder is obtained by the following method:

[0055] A coal gasifier is used to gasify coal powder with an average particle size of 60 μm, oxygen-rich gas and water vapor at 1200° C. The coal powder is allowed to stay in the coal gasifier for 10 seconds to obtain a solid product.

[0056] The volume ratio of the oxygen-rich gas to the water vapor is 18:1, the oxygen-rich gas is oxygen-rich air with an oxygen content of 25%; in the gasification reaction, 1 kg of coal powder and 1.0 m 3 The oxygen-rich gas is subjected to a gasification reaction.

[0057] Example 2

[0058] The adsorbent for treating chemical wastewater in this embodiment includes the following raw materials in parts by weight:

[0059] 40 parts of activated coke, 20 parts of gasified coal powder, 25 parts of polyaluminium chloride, 9 parts of 3,4',5-trialdehyde-1,1-biphenyl, 12 parts of triphenylene-1,5,9-triamine, and 0.5 parts of cobalt chloride.

[0060] The gasified coal powder is a solid product obtained by gasification reaction of coal powder with oxygen-rich gas and water vapor. Among the gasified coal powder, the gasified coal powder with a pore size of 50nm or more accounts for 25%. Among the activated coke, the activated coke with a pore size of 1-50nm accounts for 15%.

[0061] The preparation method of the adsorbent for treating chemical wastewater in this embodiment comprises the following steps:

[0062] Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 80° C. for 90 hours, filter and dry the crystalline precipitate to obtain the first intermediate;

[0063] The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:2000; and the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 240 g / L.

[0064] The first intermediate, cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride and modified zeolite are added into tetrahydrofuran solvent, stirred for 20 hours, and the solvent is removed to obtain;

[0065] Wherein, the concentration of the cobalt chloride in the tetrahydrofuran solvent is 15 g / L.

[0066] The gasified coal powder is obtained by the following method:

[0067] A coal gasifier is used to gasify coal powder with an average particle size of 60 μm with oxygen-rich gas and water vapor at 1250° C. The coal powder is allowed to stay in the coal gasifier for 20 seconds to obtain a solid product.

[0068] The volume ratio of the oxygen-rich gas to the water vapor is 20:1, the oxygen-rich gas is oxygen-rich air with an oxygen content of 35%; in the gasification reaction, 1 kg of coal powder is mixed with 1.2 m 3 The oxygen-rich gas is subjected to a gasification reaction.

[0069] Example 3

[0070] The adsorbent for treating chemical wastewater in this embodiment includes the following raw materials in parts by weight:

[0071] 50 parts of activated coke, 30 parts of gasified coal powder, 30 parts of polyaluminium chloride, 10 parts of 3,4',5-trialdehyde-1,1-biphenyl, 11 parts of triphenylene-1,5,9-triamine, and 1.0 part of cobalt chloride.

[0072] The gasified coal powder is a solid product obtained by gasification reaction of coal powder with oxygen-rich gas and water vapor. Among the gasified coal powder, the proportion of gasified coal powder with a pore size of 50nm or more is 35%. Among the activated coke, the proportion of activated coke with a pore size of 1-50nm is 27%.

[0073] The preparation method of the adsorbent for treating chemical wastewater in this embodiment comprises the following steps:

[0074] Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 60° C. for 10 hours, filter and dry the crystalline precipitate to obtain the first intermediate;

[0075] The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:1500; and the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100 g / L.

[0076] The first intermediate, cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride and modified zeolite are added to tetrahydrofuran solvent, stirred for 24 hours, and the solvent is removed to obtain;

[0077] Wherein, the concentration of the cobalt chloride in the tetrahydrofuran solvent is 10 g / L.

[0078] The gasified coal powder is obtained by the following method:

[0079] A coal gasifier is used to gasify coal powder with an average particle size of 60 μm, oxygen-rich gas and water vapor at 1350° C. The coal powder is allowed to stay in the coal gasifier for 15 seconds to obtain a solid product.

[0080] The volume ratio of the oxygen-rich gas to the water vapor is 16:1, the oxygen-rich gas is oxygen-rich air with an oxygen content of 30%; in the gasification reaction, 1 kg of coal powder is mixed with 0.8 m 3 The oxygen-rich gas is subjected to a gasification reaction.

[0081] Example 4

[0082] The adsorbent for treating chemical wastewater in this embodiment includes the following raw materials in parts by weight:

[0083] 35 parts of activated coke, 28 parts of gasified coal powder, 30 parts of polyaluminium chloride, 15 parts of modified zeolite, 9 parts of 3,4',5-trialdehyde-1,1-biphenyl, 12 parts of triphenylene-1,5,9-triamine, and 0.8 parts of cobalt chloride.

[0084] The gasified coal powder is a solid product obtained by gasification reaction of coal powder with oxygen-rich gas and water vapor. Among the gasified coal powder, the gasified coal powder with a pore size of 50nm or more accounts for 35%. Among the activated coke, the activated coke with a pore size of 1-50nm accounts for 30%. The modified zeolite is a zeolite with polyethyleneimine grafted on the surface.

[0085] The preparation method of the adsorbent for treating chemical wastewater in this embodiment comprises the following steps:

[0086] Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 80°C for 60 hours, filter and dry the crystalline precipitate to obtain the first intermediate;

[0087] The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:1800; and the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 200 g / L.

[0088] The first intermediate, cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride and modified zeolite are added to tetrahydrofuran solvent, stirred for 24 hours, and the solvent is removed to obtain;

[0089] Wherein, the concentration of the cobalt chloride in the tetrahydrofuran solvent is 20 g / L.

[0090] The gasified coal powder is obtained by the following method:

[0091] A coal gasifier is used to gasify coal powder with an average particle size of 60 μm with oxygen-rich gas and water vapor at 1300° C. The coal powder is allowed to stay in the coal gasifier for 20 seconds to obtain a solid product.

[0092] The volume ratio of the oxygen-rich gas to the water vapor is 18:1, the oxygen-rich gas is oxygen-rich air with an oxygen content of 30%; in the gasification reaction, 1 kg of coal powder and 1.2 m 3 The oxygen-rich gas is subjected to a gasification reaction.

[0093] The modified zeolite is obtained by the following method:

[0094] (1) adding zeolite with an average particle size of 30 μm into a hydrochloric acid solution with a concentration of 0.2 mol / L and soaking it for 5 h, filtering, washing and drying to obtain acidified zeolite;

[0095] (2) adding 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reflux reacting at 80° C. for 6 h, filtering, washing and drying to obtain a coupled polymerized zeolite;

[0096] Wherein, the mass ratio of the acidified zeolite to 3-aminopropyltrimethoxysilane is 1:0.02; and the volume ratio of the acidified zeolite to the toluene solution is 1:2.

[0097] (3) Add polyethyleneimine and formaldehyde solution to the coupled polymerized zeolite obtained in step (2), react at 60° C. for 5 h, filter, wash and dry.

[0098] 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.

[0099] Example 5

[0100] The adsorbent for treating chemical wastewater in this embodiment includes the following raw materials in parts by weight:

[0101] 35 parts of activated coke, 28 parts of gasified coal powder, 30 parts of polyaluminium chloride, 10 parts of modified zeolite, 12 parts of 3,4',5-trialdehyde-1,1-biphenyl, 12 parts of triphenylene-1,5,9-triamine, and 1.0 part of cobalt chloride.

[0102] The gasified coal powder is a solid product obtained by gasification reaction of coal powder with oxygen-rich gas and water vapor. Among the gasified coal powder, the gasified coal powder with a pore size of 50nm or more accounts for 35%. Among the activated coke, the activated coke with a pore size of 1-50nm accounts for 30%. The modified zeolite is a zeolite with polyethyleneimine grafted on the surface.

[0103] The preparation method of the adsorbent for treating chemical wastewater in this embodiment comprises the following steps:

[0104] Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 60° C. for 10 hours, filter and dry the crystalline precipitate to obtain the first intermediate;

[0105] The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:1000; and the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100 g / L.

[0106] 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, polyaluminium chloride, and modified zeolite into tetrahydrofuran solvent, stir for 24 hours, and remove the solvent to obtain;

[0107] Wherein, the concentration of the cobalt chloride in the tetrahydrofuran solvent is 10 g / L.

[0108] The gasified coal powder is obtained by the following method:

[0109] A coal gasifier is used to gasify coal powder with an average particle size of 60 μm with oxygen-rich gas and water vapor at 1300° C. The coal powder is allowed to stay in the coal gasifier for 20 seconds to obtain a solid product.

[0110] The volume ratio of the oxygen-rich gas to the water vapor is 18:1, the oxygen-rich gas is oxygen-rich air with an oxygen content of 30%; in the gasification reaction, 1 kg of coal powder and 1.2 m 3 The oxygen-rich gas is subjected to a gasification reaction.

[0111] The modified zeolite is obtained by the following method:

[0112] (1) adding zeolite with an average particle size of 30 μm into a hydrochloric acid solution with a concentration of 0.2 mol / L and soaking it for 5 h, filtering, washing and drying to obtain acidified zeolite;

[0113] (2) adding 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reflux reacting at 90° C. for 5 h, filtering, washing, and drying to obtain a coupled polymerized zeolite;

[0114] Wherein, the mass ratio of the acidified zeolite to 3-aminopropyltrimethoxysilane is 1:0.01; and the volume ratio of the acidified zeolite to the toluene solution is 1:1.5.

[0115] (3) Add polyethyleneimine and formaldehyde solution to the coupled polymerized zeolite obtained in step (2), react at 80° C. for 1 h, filter, wash and dry.

[0116] 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.

[0117] Example 6

[0118] The adsorbent for treating chemical wastewater in this embodiment includes the following raw materials in parts by weight:

[0119] 35 parts of activated coke, 28 parts of gasified coal powder, 30 parts of polyaluminium chloride, 20 parts of modified zeolite, 9 parts of 3,4',5-trialdehyde-1,1-biphenyl, 8 parts of triphenylene-1,5,9-triamine, and 0.5 parts of cobalt chloride.

[0120] The gasified coal powder is a solid product obtained by gasification reaction of coal powder with oxygen-rich gas and water vapor. Among the gasified coal powder, the gasified coal powder with a pore size of 50nm or more accounts for 35%. Among the activated coke, the activated coke with a pore size of 1-50nm accounts for 30%. The modified zeolite is a zeolite with polyethyleneimine grafted on the surface.

[0121] The preparation method of the adsorbent for treating chemical wastewater in this embodiment comprises the following steps:

[0122] Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 80° C. for 90 hours, filter and dry the crystalline precipitate to obtain the first intermediate;

[0123] The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:2000; and the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 240 g / L.

[0124] The first intermediate, cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride and modified zeolite are added to tetrahydrofuran solvent, stirred for 24 hours, and the solvent is removed to obtain;

[0125] Wherein, the concentration of the cobalt chloride in the tetrahydrofuran solvent is 20 g / L.

[0126] The gasified coal powder is obtained by the following method:

[0127] A coal gasifier is used to gasify coal powder with an average particle size of 60 μm with oxygen-rich gas and water vapor at 1300° C. The coal powder is allowed to stay in the coal gasifier for 20 seconds to obtain a solid product.

[0128] The volume ratio of the oxygen-rich gas to the water vapor is 18:1, the oxygen-rich gas is oxygen-rich air with an oxygen content of 30%; in the gasification reaction, 1 kg of coal powder and 1.2 m 3 The oxygen-rich gas is subjected to a gasification reaction.

[0129] The modified zeolite is obtained by the following method:

[0130] (1) adding zeolite with an average particle size of 30 μm into a hydrochloric acid solution with a concentration of 0.2 mol / L and soaking it for 5 h, filtering, washing and drying to obtain acidified zeolite;

[0131] (2) adding 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reflux reacting at 100° C. for 8 h, filtering, washing and drying to obtain a coupled polymerized zeolite;

[0132] Wherein, 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.

[0133] (3) Add polyethyleneimine and formaldehyde solution to the coupled polymerized zeolite obtained in step (2), react at 50° C. for 12 h, filter, wash and dry.

[0134] 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.

[0135] Example 7

[0136] The adsorbent for treating chemical wastewater in this comparative example is the same as that in Example 4, except that 4 parts by weight of nonylphenol polyoxyethylene ether is also included.

[0137] The preparation method of the adsorbent for treating chemical wastewater in this embodiment is the same as that in Example 4, except that it further includes the step of adding nonylphenol polyoxyethylene ether, which is specifically as follows:

[0138] Take 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine, mix them evenly, and react to obtain a 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.

[0139] Comparative Example 1

[0140] The adsorbent used for treating chemical wastewater in this comparative example is the same as that in Example 4 and is prepared by the same method, with the only difference being that it does not contain gasified coal powder.

[0141] Comparative Example 2

[0142] The adsorbent for treating chemical wastewater in this comparative example is the same as that in Example 4 and is prepared by the same method, with the only difference being that the modified zeolite is replaced by an unmodified zeolite.

[0143] Comparative Example 3

[0144] The adsorbent for treating chemical wastewater in this comparative example is the same as that in Example 4 and is prepared by the same method. The only difference is that the preparation method of the modified zeolite is different.

[0145] In step (2) of the modified zeolite preparation method of 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 coupled polymerized zeolite to polyethyleneimine is 1:0.08.

[0146] Comparative Example 4

[0147] The adsorbent for treating chemical wastewater in this comparative example is the same as that in Example 4 and is prepared by the same method. The only difference is that the preparation method of the modified zeolite is different.

[0148] In step (2) of the modified zeolite preparation method of 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 coupled polymerized zeolite to polyethyleneimine is 1:0.01.

[0149] Comparative Example 5

[0150] The adsorbent for treating chemical wastewater in this comparative example is the same as that in Example 4 and is prepared by the same method. The only difference is that the preparation method of the modified zeolite is different, as follows:

[0151] (1) adding zeolite with an average particle size of 30 μm into a hydrochloric acid solution with a concentration of 0.2 mol / L and soaking it for 5 h, filtering, washing and drying to obtain acidified zeolite;

[0152] (2) Add polyethyleneimine and formaldehyde solution to the acidified zeolite obtained in step (1), react at 60° C. for 5 h, filter, wash and dry.

[0153] 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.

[0154] Comparative Example 6

[0155] The adsorbent for treating chemical wastewater in this comparative example is the same as that in Example 4 and is prepared by the same method, the only difference being that the modified zeolite is not contained.

[0156] Comparative Example 7

[0157] This comparative example is the same as the adsorbent for treating chemical wastewater in Example 7 and is prepared by the same method, the only difference being that the comparative example does not contain the polyaluminium chloride.

[0158] Comparative Example 8

[0159] This comparative example is the same as the adsorbent for treating chemical wastewater in Example 7 and is prepared by the same method, the only difference being that it does not contain the 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine.

[0160] Effect experiment example

[0161] In order to verify the technical effect of the adsorbent for treating chemical wastewater described in the present invention, the following experiments were conducted:

[0162] Take the coking wastewater to be treated, and measure the COD concentration of the coking wastewater to be 162 mg / L and the ammonia nitrogen concentration to be 236 mg / L. Then take 10 g of the adsorbent for treating chemical wastewater prepared in Examples 1-7 and Comparative Examples 1-8 as samples, add them into 800 ml of coking wastewater respectively, and continue stirring. After 30 min and 6 h, the COD concentration and ammonia nitrogen concentration after treatment are measured, and the COD removal rate and ammonia nitrogen removal rate are calculated.

[0163] After experimentation, the results are as follows:

[0164]

[0165] According to the above experimental results, the adsorbent for treating chemical wastewater described in the present invention can achieve good adsorption and removal effects on organic pollutants and ammonia nitrogen inorganic ions in the wastewater.

[0166] According to the results of Examples 1-3, Examples 4-6, and Comparative Example 6, the addition of the modified zeolite improves the COD removal rate and the ammonia nitrogen removal rate. According to the results of Example 4 and Comparative Example 1, the addition of the gasified coal powder has a significant effect on improving the COD removal rate and the ammonia nitrogen removal rate. According to the results of Examples 1-4 and Comparative Example 2, the unmodified zeolite has no obvious effect on improving the COD removal rate and the ammonia nitrogen removal rate.

[0167] According to the results of Example 4 and Comparative Example 5, the modified zeolite that is not coupled with the 3-aminopropyltrimethoxysilane has a COD removal rate and ammonia nitrogen removal rate after 30 minutes of treatment, which are not much different from those of Example 4, but the COD removal rate and ammonia nitrogen removal rate after 6 hours of treatment are greatly reduced, and the performance is significantly reduced. According to the results of Example 4 and Comparative Examples 3-4, the amount of 3-aminopropyltrimethoxysilane and polyethyleneimine used in the preparation process of the modified zeolite has a greater impact on the effect of the adsorbent, that is, the grafting rate of the modified zeolite has a significant impact on the effect of the adsorbent. When the grafting rate is too low, the COD removal rate and ammonia nitrogen removal rate are not significantly improved. When the grafting rate is too high, the COD removal rate and ammonia nitrogen removal rate are reduced to a certain extent.

[0168] According to the results of Examples 4 and 7 and Comparative Example 7, the addition of the polyaluminium chloride significantly improves the removal rate and speed of COD and ammonia nitrogen molecules. The addition of the nonylphenol polyoxyethylene ether greatly improves the ammonia nitrogen removal rate after 30 minutes of adsorbent treatment, and the COD removal rate after 30 minutes of treatment also slightly increases, which can accelerate the removal of ammonia nitrogen molecules and organic pollutants, especially ammonia nitrogen molecules. The synergistic use of the two can greatly improve the comprehensive adsorption effect.

[0169] According to the results of Example 7 and Comparative Example 8, the addition of 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine has a greater effect on the removal rate of ammonia nitrogen molecules, but a weaker effect on the COD removal rate. It can be seen that the metal-organic cage polymer formed by 3,4',5-trialdehyde-1,1-biphenyl, triphenylene-1,5,9-triamine and cobalt chloride is selective for ammonia nitrogen molecules and has a significant enhancement effect on the removal of ammonia nitrogen molecules.

[0170] It can be seen that the adsorbent for treating chemical wastewater described in the present invention, which uses the activated coke, gasified coal powder, polyaluminum chloride, modified zeolite, 3,4',5-trialdehyde-1,1-biphenyl, phenylene-1,5,9-triamine, cobalt chloride, and nonylphenol polyoxyethylene ether, can synergistically exert an adsorption effect and effectively remove organic pollutants and ammonia nitrogen inorganic ions in coking wastewater with complex components.

[0171] It is known from common technical knowledge that the present invention can be implemented by other embodiments that do not deviate from its spirit or essential features. Therefore, the above disclosed embodiments are only illustrative in all respects and are not exclusive. All changes within the scope of the present invention or within the scope equivalent to the present invention are encompassed by the present invention.

Claims

1. An adsorbent for treating chemical wastewater, characterized in that: The invention comprises the following raw materials in parts by weight: 30-50 parts of activated coke, 20-30 parts of gasified coal powder, 25-35 parts of polyaluminium chloride, 10-20 parts of modified zeolite, 8-10 parts of 3,4',5-trialdehyde-1,1-biphenyl, 10-12 parts of triphenylene-1,5,9-triamine, 0.5-1.0 parts of cobalt chloride, 3-5 parts of nonylphenol polyoxyethylene ether; The method for preparing the adsorbent for treating chemical wastewater comprises the following steps: Take 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine, mix them evenly, and react to obtain a first intermediate; mix the first intermediate with cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride, modified zeolite and nonylphenol polyoxyethylene ether evenly to obtain; Wherein, the modified zeolite is a zeolite with polyethyleneimine grafted on the surface; the modified zeolite is obtained by the following method: (1) adding zeolite to a hydrochloric acid solution with a concentration of 0.1-0.3 mol / L and soaking it for 3-5 hours, filtering, washing, and drying to obtain an acidified zeolite; (2) adding 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reacting at 80-100° C. for 5-8 hours, filtering, washing, and drying to obtain a coupled polymerized zeolite; (3) adding polyethyleneimine and formaldehyde solution to the coupled polymerized zeolite obtained in step (2), reacting at 50-80° C. for 1-12 h, filtering, washing, and drying; The first intermediate is obtained by the following method: Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 50-80° C. for 10-90 hours, filter and dry the crystalline precipitate to obtain the first intermediate; The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:(1000-2000); the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100-240 g / L.

2. The adsorbent for treating chemical wastewater according to claim 1, characterized in that: 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 wastewater according to claim 2, characterized in that: Among the gasified coal powder, the gasified coal powder with a pore size of 50 nm or more accounts for greater than or equal to 20%.

4. The adsorbent for treating chemical wastewater according to claim 3, characterized in that: Among the activated cokes, the active cokes with pore diameters in the range of 1-50 nm account for 15%-30%.

5. A method for preparing an adsorbent for treating chemical wastewater according to any one of claims 1 to 4, characterized in that: The steps include: Take 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine, mix them evenly, and react to obtain a first intermediate; mix the first intermediate with cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride, modified zeolite and nonylphenol polyoxyethylene ether evenly to obtain; The modified zeolite is obtained by the following method: (1) adding zeolite to a hydrochloric acid solution with a concentration of 0.1-0.3 mol / L and soaking it for 3-5 hours, filtering, washing, and drying to obtain an acidified zeolite; (2) adding 3-aminopropyltrimethoxysilane and toluene solution to the acidified zeolite obtained in step (1), reacting at 80-100° C. for 5-8 hours, filtering, washing, and drying to obtain a coupled polymerized zeolite; (3) adding polyethyleneimine and formaldehyde solution to the coupled polymerized zeolite obtained in step (2), reacting at 50-80° C. for 1-12 h, filtering, washing, and drying; The first intermediate is obtained by the following method: Add 3,4',5-trialdehyde-1,1-biphenyl and triphenylene-1,5,9-triamine to tetrahydrofuran solvent, add sulfuric acid, react at 50-80° C. for 10-90 hours, filter and dry the crystalline precipitate to obtain the first intermediate; The molar ratio of the sulfuric acid to the 3,4',5-trialdehyde-1,1-biphenyl is 1:(1000-2000); the concentration of the 3,4',5-trialdehyde-1,1-biphenyl in the tetrahydrofuran solvent is 100-240 g / L.

6. The method for preparing an adsorbent for treating chemical wastewater according to claim 5, characterized in that: The gasified coal powder is obtained by the following method: the coal powder is subjected to a gasification reaction with oxygen-rich gas and water vapor at 1200-1350° C. 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, 1 kg of coal powder is mixed with 0.8-1.2 m 3 The oxygen-rich gas is subjected to a gasification reaction.

7. The method for preparing an adsorbent for treating chemical wastewater according to claim 5, characterized in that: The method also includes the steps of grinding the activated coke, gasified coal powder and modified zeolite and passing the mixture through a 200-325 mesh sieve.

8. The method for preparing an adsorbent for treating chemical wastewater according to claim 7, characterized in that: The first intermediate is mixed evenly with cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride, modified zeolite and nonylphenol polyoxyethylene ether, specifically comprising: The first intermediate, cobalt chloride, activated coke, gasified coal powder, polyaluminium chloride, modified zeolite and nonylphenol polyoxyethylene ether are added to tetrahydrofuran solvent, stirred for 12-24 hours, and the solvent is removed to obtain; Wherein, the concentration of the cobalt chloride in the tetrahydrofuran solvent is 10-20 g / L.

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