Background
With the development of petrochemical industry and related industries, organic wastewater has become one of the main water pollution sources. The organic wastewater has complex components and large organic matter content, most of the organic wastewater exists in the form of taking aromatic groups such as benzene, naphthalene, anthracene, quinone and the like as parent bodies, has deep chroma, strong toxicity and difficult degradationAnd the like, which poses increasingly serious threat to water environment. In addition, with the rapid development of industry and the unreasonable discharge of wastewater, the pollution of heavy metals in water bodies is more and more serious, the heavy metal wastewater mainly comes from the industries of mining, smelting, electronics, electroplating, pesticides, pigment manufacturing and the like, one or two heavy metal pollutants are mainly used, and various inorganic and organic pollutants coexist. Heavy metal pollution is toxic, difficult to metabolize in the environment, easy to bio-enrich and easy to enter human body through food chain, thus seriously harming human health. In some special bodies of water, there is also an excess of F-And also poses a threat to human health.
At present, more treatment methods aiming at the organic and heavy metal polluted wastewater comprise an oxidation method, a photocatalysis method, a coagulation method, a membrane separation method, an adsorption method and the like. The above treatment methods have advantages and disadvantages, and the adsorption method is simple to operate and widely used.
CN 201310733073.7 provides a method for treating methylene blue dye wastewater, which takes diatomite and the like as raw materials to prepare an adsorbent loaded with yeast to treat dye organic wastewater. The mullite, analcite and diatomite adsorbents used in the method have low specific surface area and limited absorption capacity for various organic molecular pollutants. Meanwhile, the yeast used cannot degrade inorganic metal ions. CN201510688988.X provides a modified walnut shell activated carbon adsorbent and a preparation method thereof, which are mainly used for adsorption and removal of heavy metal ions and have limited effect on organic pollutants.
The adsorption material adopted by the existing adsorption method for treating industrial sewage generally has the following defects: the saturated adsorption capacity of different adsorption materials is different and is limited by the pore structure and the surface structure of the adsorbent, and the adsorption material with single property can hardly treat a wide range of organic and inorganic pollutants with different properties in the water body. Therefore, it is important to develop an adsorbent that can co-treat organic and inorganic wastewater simply and efficiently.
Disclosure of Invention
Aiming at the existing defects, the invention provides a composite adsorbing material which can adsorb various organic pollutants, heavy metal ions and other harmful ions in wastewater in a broad spectrum manner.
The composite adsorbing material comprises, by weight, 5% -50% of coal dust, 10% -50% of activated carbon and 5% -60% of nano analcite; wherein the fly ash and the analcime are connected into a whole through activated carbon; the specific surface area of the composite adsorbing material is 300-1500m2Per g, pore volume of 0.3-1.5cm3(ii) a mechanical strength of 5 to 25N/mm.
In the composite adsorbing material, the granularity of the coal dust is 100-1000 meshes, preferably 300-800 meshes; the pore size of the fly ash is 1 to 200 μm, preferably 10 to 100. mu.m.
In the composite adsorbing material, the nano-analcime crystal particles are nearly spherical, and the diameter is 10-200nm, preferably 20-100 nm.
The preparation method of the composite adsorbing material comprises the following steps:
preparation of nano-cubic zeolite
(1) Uniformly mixing a silicon source, an alkali source, N-methylpyrrolidine and water, sealing, carrying out hydrothermal treatment, cooling the material to room temperature, adding an aluminum source into the material after the hydrothermal treatment, and uniformly mixing;
(2) and (2) aging, crystallizing, washing, drying and roasting the material obtained in the step (1) to obtain the nano analcime.
The alkali source in the step (1) is alkali metal hydroxide, preferably sodium hydroxide.
The silicon source in the step (1) is one or a composition of silica sol, silica gel, white carbon black, water glass, ethyl silicate-28, ethyl silicate-32 or ethyl silicate-40, diatomite and silicon alkoxide, and preferably one or more of silica sol, white carbon black, ethyl silicate-28, ethyl silicate-32 or ethyl silicate-40.
The aluminum source in the step (1) is one or a combination of sodium metaaluminate, aluminum nitrate, aluminum chloride, aluminum sulfate, aluminum oxide, aluminum hydroxide and organic aluminum alkoxide, preferably one or more of sodium metaaluminate, aluminum isopropoxide and aluminum sec-butoxide.
The mixing mode in the step (1) is any one of mechanical stirring, magnetic stirring or oscillation.
The alkali source, the aluminum source, the water, the silicon source and the N-methylpyrrolidine in the step (1) are calculated by the following substances, and the proportional relation is satisfied:
SiO2/Al2O3the molar ratio is 5-80
N-methylpyrrolidine/SiO2The molar ratio is 0.05-0.25
H2O/SiO2The molar ratio is 20-100
OH-/SiO2The molar ratio is 0.5-0.9
The closed hydrothermal treatment conditions in the step (1) are as follows: sealing and hydrothermally treating at 90-120 deg.C for 1-24 hr.
The aging conditions in the step (2) are as follows: the aging temperature is 30-80 ℃, the aging time is 0.5-10 hours, preferably 1-6 hours, more preferably 2-5 hours, the aging is carried out under the stirring condition, and further preferably the aging is carried out under the combined action of ultrasonic dispersion and stirring; wherein the ultrasonic conditions are: the energy density of ultrasonic dispersion is 0.2-4kW/L, and the time of ultrasonic and stirring action is 2-5 hours; the stirring mode comprises mechanical stirring and/or magnetic stirring.
The crystallization process in the step (2) is carried out in a reaction kettle, and the crystallization conditions are as follows: the crystallization temperature is 140-200 ℃, preferably 160-190 ℃, the crystallization reaction is 5-250 hours, preferably 72-170 hours, and the pressure is the autogenous pressure of the reaction kettle.
The washing, drying and roasting processes of the product in the method are conventional processes in the field, and the treatment conditions adopted by the method are as follows: washing the reaction product to neutrality with distilled water, and drying at 80-150 deg.c for 5-24 hr at 500-800 deg.c for 2-10 hr.
And (II) uniformly mixing the coal dust and the nano analcime, then adding a phenolic resin solution, kneading into a sticky mass, then molding, and carbonizing the molded product at high temperature to obtain the composite adsorbing material.
Carbonization conditions: under the protection of inert gas, the temperature is raised to 600-1000 ℃, the temperature raising rate is 0.1-20 ℃/min, and the carbonization time is 3-12 hours. And cooling to obtain the composite adsorbing material.
The coal ash contained in the composite adsorbent disclosed by the invention has a natural multistage pore structure, large-size components such as colloid and macromolecular organic matters in filtered wastewater are facilitated, a carbon material formed after phenolic resin in the adsorbent is carbonized has a developed pore structure and can be used for adsorbing small-molecular organic matters and metal ions, the superfine analcite belongs to a nano-scale small grain size, the small-molecular organic matters and the metal ions can be further deeply adsorbed by the developed outer surface, and the specific pore size of the analcite can further expand the range of adsorbable molecules. Therefore, the multi-stage pore composite water treatment material can simultaneously realize the effective adsorption and removal of various organic and inorganic pollutants with different properties in industrial wastewater in a broad spectrum manner, and the method is simple and easy to operate.
Detailed Description
The process of the present invention is illustrated in detail by the following examples. The crystal form of the analcime is represented by X-ray diffraction, and the appearance and the size are observed and measured by a scanning electron microscope. The specific surface area is measured by a low-temperature nitrogen adsorption method. The mechanical strength was determined according to HG/T2782-.
Example 1
Mixing water, sodium hydroxide, silica sol and N-methylpyrrolidine according to a certain proportion at room temperature, then sealing and heating the mixture for 24 hours at 90 ℃, cooling the mixture to room temperature, adding the standby sodium metaaluminate powder into the solution, and uniformly stirring the mixture. The final material proportion meets the following requirements: al (Al)2O3/SiO2=30, N-methylpyrrolidine/SiO2=0.15,OH-/SiO2=0.75,H2O/SiO2= 40. Then the mixture is treated by ultrasonic (1.0 KW/L) and magnetic stirring for 3 hours at 40 ℃, and then the mixture is put into a reaction kettle to be crystallized for 120 hours at 175 ℃. The obtained product is washed by distilled water, dried at 120 ℃ and roasted at 550 ℃ for 5 hours. XRD detection proves that the analcime is analcime, and is in spherical form, and the grain size is about 30nm, and belongs to superfine nano-grade range, and its specific surface area is 270m2(ii) in terms of/g. Uniformly mixing 200 meshes of coal ash (containing 10-100 mu m of macropores and super macropores) with superfine analcime (the mass ratio of the coal ash to the analcime is 1: 1), fully infiltrating with 20% of phenolic resin solution, then blending, kneading into a sticky mass, then extruding into a cylinder with the diameter of 2mm by using a forming device, drying, and carbonizing for 6 hours at 800 ℃ under the protection of nitrogen to obtain the coal ash-analcime-carbon ternary composite material. The composite material contains 30% of coal ash and 30% of analcime by weight, and the balance of carbon. The specific surface area of the composite material is 629 m2Per g, pore volume of 0.51cm3(ii)/g, mechanical strength 11N/mm. The adsorption properties are shown in Table 1.
Example 2
Mixing water, sodium hydroxide, silica sol and N-methylpyrrolidine according to a certain proportion at room temperature, then sealing and heating the mixture for 24 hours at 100 ℃, cooling the mixture to room temperature, adding the standby sodium metaaluminate powder into the solution, and uniformly stirring the mixture. The final material proportion meets the following requirements: al (Al)2O3/SiO2=40, N-methylpyrrolidine/SiO2=0.20,OH-/SiO2=0.8,H2O/SiO2= 60. Then the mixture is treated by ultrasonic treatment (0.5 KW/L) at 60 ℃ and stirred for 3 hours, and then the mixture is put into a reaction kettle to be crystallized for 140 hours at 180 ℃. The obtained product is washed by distilled water, dried at 120 ℃ and roasted at 550 ℃ for 5 hours. The product is proved to be analcite by XRD detection, is in a spherical shape by observation of a scanning electron microscope, has the grain size of about 35nm, belongs to a nanoscale range, and has the specific surface area of 212m2(ii) in terms of/g. Mixing 500 mesh coal ash (containing 10-100 μm macropores and super macropores) with superfine analcime (mass ratio of coal ash to analcime is 1: 1), adding 20% phenolic resin solutionMixing the solution, fully wetting, blending, kneading into a sticky mass, extruding into a cylinder with the diameter of 2mm by using molding equipment, drying, and carbonizing for 6 hours at 900 ℃ under the protection of nitrogen to obtain the coal ash-analcite-carbonaceous ternary composite material. The composite material contains 35% of pulverized coal ash, 35% of analcime and the balance of carbonaceous materials. The specific surface area of the composite material is 1056 m2Per g, pore volume of 0.67cm3(ii)/g, mechanical strength 14N/mm. The adsorption properties are shown in Table 1.
Example 3
Mixing water, sodium hydroxide, silica sol and N-methylpyrrolidine according to a certain proportion at room temperature, then sealing and carrying out hydrothermal treatment at 120 ℃ for 6 hours, cooling to room temperature, adding isopropanol aluminum powder into the solution, and uniformly stirring. The final material proportion meets the following requirements: al (Al)2O3/SiO2=60, N-methylpyrrolidine/SiO2=0.25,OH-/SiO2=0.9,H2O/SiO2= 80. Then the mixture is treated by ultrasonic (2.0 KW/L) and magnetic stirring for 3 hours at 50 ℃, and then the mixture is put into a reaction kettle to be crystallized for 140 hours at 180 ℃. The obtained product is washed by distilled water, dried at 120 ℃ and roasted at 550 ℃ for 5 hours. The product is proved to be analcite by XRD detection, is in a spherical shape by observation of a scanning electron microscope, has the grain size of about 18nm, belongs to an ultra-fine nanometer range and has the specific surface area of 380m2(ii) in terms of/g. Uniformly mixing 500-mesh coal ash (containing 10-100 mu m macropores and super macropores) with superfine analcime (the mass ratio of the coal ash to the analcime is 1: 2), then fully wetting the mixture by using 20% of phenolic resin solution, blending and kneading the mixture into a sticky mass, then extruding the sticky mass into a cylinder with the diameter of 2mm by using a forming device, drying the cylinder, and carbonizing the cylinder for 6 hours at 900 ℃ under the protection of nitrogen to obtain the coal ash-analcime-carbon ternary composite material. The composite material contains 20% of coal ash, 40% of analcime and the balance of carbonaceous materials. The specific surface area of the composite material is 1347 m2Per g, pore volume of 0.78cm3(ii) g, mechanical strength 15N/mm. The adsorption properties are shown in Table 1.
Comparative example 1
An adsorbent material was prepared as in example 1 of CN 201310733073.7. The adsorption properties are shown in Table 1.
Comparative example 2
The adsorbent material was prepared as in example 1 in cn201510688988. x. The adsorption properties are shown in Table 1.
Comparative example 3
The fly ash, ultrafine analcite and the same amount of phenolic resin used in example 1 were mixed mechanically to prepare an adsorbent. The adsorption properties are shown in Table 1.
TABLE 1 comparison of adsorption Properties of adsorption materials on simulated Industrial wastewater
Simulating the composition of industrial sewage: the concentration of methylene blue is 2000mg/L, the concentration of mercuric chloride is 200mg/L, the concentration of lead nitrate is 200mg/L, and the concentration of sodium fluoride is 10 mg/L. The mass ratio of the adsorbent to the simulated sewage is 1: 250 at the adsorption temperature of 25 ℃ at room temperature, and the adsorption treatment time is 30 minutes.