CN112844327B - Sewage treatment adsorbent and preparation method thereof - Google Patents
Sewage treatment adsorbent and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
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Abstract
The invention discloses a sewage treatment adsorbent which comprises the following raw materials in parts by weight: 35-50 parts of composite filler, 15-30 parts of high-adsorption kaolin and 5-15 parts of chitosan; the sewage treatment adsorbent is prepared by the following method: adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, carrying out ball milling for 1h at the rotating speed of 450-plus-one 500r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent; the invention also discloses a preparation method of the sewage treatment adsorbent; the second intermediate is an 8-hydroxyquinoline derivative, and then the modified intermediate and the second intermediate are mixed in absolute ethyl alcohol in step S4, and the second intermediate is grafted on the inner surface of the modified intermediate, so that the 8-hydroxyquinoline derivative has excellent antibacterial performance, and the finally prepared composite filler is endowed with metal chelation and antibacterial performance.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a sewage treatment adsorbent and a preparation method thereof.
Background
Many mechanical equipment processing and manufacturing enterprises, such as enterprises of electroplating, hardware, circuit board production and the like, discharge production wastewater which contains a large amount of heavy metals, wherein the heavy metals generally refer to metals with specific gravity greater than 4 or 5, and about 45 types of heavy metals are selected, such as copper, lead, zinc, iron, cobalt, nickel, vanadium, ni, shoulder, barium, manganese, fluorine, mercury, tungsten, aluminum, gold, silver and the like; although heavy metals such as manganese, copper and zinc are trace elements required by life activities, most heavy metals such as mercury, lead and fortune are necessary for non-life activities, and all heavy metals are toxic to human bodies when exceeding a certain concentration, and if the heavy metal-containing sewage is not treated and is directly discharged in the natural environment, the heavy metal-containing sewage causes serious heavy metal environmental pollution.
The Chinese invention patent CN103723852A discloses a sewage treatment method based on inorganic and organic heavy metal adsorbents, which comprises the following steps: putting sewage into a pH value adjusting water tank, introducing the adjusted sewage into a reaction tower, filling air into the reaction tower, and adding a catalyst into the reaction tower, wherein the catalyst is scrap iron and active carbon; then, introducing the sewage passing through the reaction tower into a sedimentation tank, adding an inorganic heavy metal adsorbent into the sedimentation tank, introducing the sewage into a pipeline mixer, and adding an organic heavy metal adsorbent; and then, enabling the sewage in the pipeline mixer to enter a solid-liquid separator, precipitating and depositing heavy metal-containing solid impurities in the sewage at the bottom of the solid-liquid separator, and discharging liquid in the sewage after passing through the solid-liquid separator.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a sewage treatment adsorbent and a preparation method thereof.
The existing sewage treatment adsorbent can treat single metal ions in sewage, but cannot be used for multiple metal ions and has no antibacterial performance, the intermediate is modified by 3-aminopropyltriethoxysilane in step S2, amino is introduced to the intermediate to prepare a modified intermediate, the amino is introduced to chelate heavy metal ions in sewage to form a stable coordination compound, the application range of the stable coordination compound is further expanded, multiple heavy metal ions are removed, 8-hydroxyquinoline, ethanol, trichloromethane and sodium hydroxide are mixed in step S3 to prepare a second intermediate, the second intermediate is an 8-hydroxyquinoline derivative, then the modified intermediate and the second intermediate are mixed in absolute ethanol in step S4, and the second intermediate is grafted on the inner surface of the modified intermediate, the 8-hydroxyquinoline derivative has excellent antibacterial performance, and endows the finally prepared composite filler with metal chelation and antibacterial performance.
The purpose of the invention can be realized by the following technical scheme:
the sewage treatment adsorbent is characterized by comprising the following raw materials in parts by weight: 35-50 parts of composite filler, 15-30 parts of high-adsorption kaolin and 5-15 parts of chitosan;
the sewage treatment adsorbent is prepared by the following method:
adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, ball-milling for 1h at the rotating speed of 450-plus-one 500r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
Further, the composite filler is prepared by the following method:
step S1, adding P123 and dilute hydrochloric acid with the concentration of 2mol/L into a three-neck flask, adding deionized water after uniform mixing, heating to 30-40 ℃, stirring at constant speed until P123 is completely dissolved, then dropwise adding ethyl orthosilicate, controlling the dropwise adding speed to be 1 drop/1 second, stirring at constant speed of 100 plus 200r/min for 20h after the dropwise adding is finished to prepare a reactant, adding the reactant into a reaction kettle with a polytetrafluoroethylene lining, heating to 80-100 ℃, standing at the temperature for crystallization for 24h, taking out, washing with deionized water for three times, filtering, drying in a drying oven at 45-60 deg.C for 20 hr to obtain crude product, adding the crude product into an extractor, refluxing acidified ethanol for 24h, then washing the acidified ethanol to be neutral by deionized water, and drying the washed acidified ethanol to obtain an intermediate, wherein the dosage ratio of P123, dilute hydrochloric acid, deionized water and tetraethoxysilane is controlled to be 2 g: 60 mL: 8-10 mL: 4 g;
s2, activating the intermediate prepared in the step S1 for 6 hours in vacuum at the temperature of 100-120 ℃, adding the activated intermediate into anhydrous toluene, dispersing the intermediate for 30 minutes at a high speed of 500r/min at the speed of 450-500r/min, dropwise adding 3-aminopropyltriethoxysilane, continuously dispersing the intermediate for 30 minutes, refluxing the intermediate for 2 hours in a nitrogen atmosphere, filtering the mixture, washing the mixture by using a first mixed solution to remove unreacted 3-aminopropyltriethoxysilane, refluxing the mixture for 12 hours by using a Soxhlet extractor by using a second mixed solution, performing suction filtration, and drying the mixture for 10 hours in vacuum at the temperature of 45-60 ℃ to prepare a modified intermediate, wherein the use ratio of the intermediate to the 3-aminopropyltriethoxysilane is controlled to be 1 g: 1 mL;
step S3, adding 8-hydroxyquinoline and ethanol into a sodium hydroxide aqueous solution with the mass fraction of 45%, dropwise adding chloroform after uniformly mixing, controlling the dropwise adding time to be 10min, refluxing for 10h under a nitrogen atmosphere after dropwise adding, rotationally evaporating unreacted ethanol, chloroform and deionized water after reaction is finished to prepare a reaction product, adding the reaction product into deionized water, dropwise adding 0.1mol/L diluted hydrochloric acid after uniformly stirring for 30min to adjust the pH until the pH is 6-6.5, extracting and drying to prepare a second intermediate, and controlling the dosage ratio of 8-hydroxyquinoline, ethanol, the sodium hydroxide aqueous solution and the chloroform to be 25 g: 100 mL: 60 mL: 25 mL;
and step S4, adding the modified intermediate and the second intermediate into a three-neck flask, adding absolute ethyl alcohol, uniformly mixing, heating and refluxing for 10 hours under a nitrogen atmosphere, filtering after the reaction is finished, washing with the absolute ethyl alcohol for three times, and drying for 10 hours under vacuum at 50-80 ℃ to prepare the composite filler, wherein the weight ratio of the modified intermediate to the second intermediate is controlled to be 4: 3.
In the step S1, P123 and tetraethoxysilane are mixed, P123 is used as a template agent, tetraethoxysilane is used as a silicon source, crystallization and calcination are carried out after mixing, the template agent is removed, an intermediate is prepared, the intermediate is an ordered mesoporous material, single ions in sewage can be adsorbed, the function is single, and other metal ions in the sewage cannot be adsorbed, the intermediate is modified through 3-aminopropyltriethoxysilane in the step S2, amino is introduced into the intermediate to prepare the modified intermediate, the amino is introduced to chelate heavy metal ions in the sewage to form a stable coordination compound, the application range of the coordination compound is further expanded, various heavy metal ions are removed, in the step S3, 8-hydroxyquinoline, ethanol, trichloromethane and sodium hydroxide are mixed to prepare a second intermediate, the second intermediate is an 8-hydroxyquinoline derivative, and then in step S4, mixing the modified intermediate and a second intermediate in absolute ethyl alcohol, grafting the second intermediate on the inner surface of the modified intermediate, wherein the 8-hydroxyquinoline derivative has excellent antibacterial performance and endows the finally prepared composite filler with metal chelation and antibacterial performance.
Further, the first mixed solution is formed by mixing toluene and dichloromethane according to the volume ratio of 1: 1, the second mixed solution is formed by mixing diethyl ether and dichloromethane according to the volume ratio of 1: 1, and the acidified ethanol is formed by mixing hydrochloric acid with the mass fraction of 35% and absolute ethanol according to the volume ratio of 3: 50.
Further, the high adsorption kaolin is prepared by the following method:
uniformly mixing kaolin and potassium acetate according to the weight ratio of 1: 1, adding deionized water for mixing, carrying out mild grinding for 30min, standing for 20h, drying in a water bath kettle at 55-60 ℃ for 10h to obtain treated kaolin, adding the treated kaolin into a hydrochloric acid solution with the mass fraction of 10%, magnetically stirring at the rotating speed of 120r/min for 20min, carrying out suction filtration, washing with absolute ethyl alcohol for three times, and transferring to a drying box at 55-60 ℃ for drying for 20h to obtain the high-adsorption kaolin.
The kaolin and the potassium acetate are uniformly mixed according to the weight ratio of 1: 1, then deionized water is added, acetate ions can be inserted into the interlayer position of the kaolin, the interlayer spacing of the kaolin is enlarged, then the kaolin is added into a hydrochloric acid solution with the mass fraction of 10%, the potassium acetate ions are removed through acid washing, the kaolin still keeps the structure, the kaolin has larger interlayer spacing, and the adsorption performance of the kaolin is improved.
A preparation method of a sewage treatment adsorbent comprises the following steps:
adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, ball-milling for 1h at the rotating speed of 450-plus-one 500r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
The invention has the beneficial effects that:
(1) the invention relates to a sewage treatment adsorbent which is prepared from raw materials such as a composite filler and high-adsorption kaolin, wherein in the preparation process of the composite filler, in step S1, P123 and tetraethoxysilane are mixed, the P123 is used as a template agent, the tetraethoxysilane is used as a silicon source, the mixture is crystallized and calcined to remove the template agent to prepare an intermediate, the intermediate is an ordered mesoporous material and can adsorb single ions in sewage, the function is single, and the rest metal ions in the sewage cannot be adsorbed, in step S2, the intermediate is modified by 3-aminopropyltriethoxysilane, amino is introduced to the intermediate to prepare the modified intermediate, the amino is introduced to chelate the heavy metal ions in the sewage to form a stable coordination compound, so that the application range of the adsorbent is expanded, and a plurality of heavy metal ions are removed, in the step S3, 8-hydroxyquinoline, ethanol, chloroform and sodium hydroxide are mixed to prepare a second intermediate, the second intermediate is an 8-hydroxyquinoline derivative, then the modified intermediate and the second intermediate are mixed in absolute ethanol in the step S4, the second intermediate is grafted on the inner surface of the modified intermediate, and the 8-hydroxyquinoline derivative has excellent antibacterial performance and endows the finally prepared composite filler with metal chelation and antibacterial performance.
(2) In the preparation process of the high-adsorption kaolin, kaolin and potassium acetate are uniformly mixed according to the weight ratio of 1: 1, then deionized water is added, acetate ions can be inserted into interlayer positions of the kaolin to enlarge the interlayer spacing of the kaolin, then the high-adsorption kaolin is added into a hydrochloric acid solution with the mass fraction of 10%, the potassium acetate ions are removed through acid washing, the structure of the kaolin is still kept, the kaolin has larger interlayer spacing, and the adsorption performance of the kaolin is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The sewage treatment adsorbent is characterized by comprising the following raw materials in parts by weight: 35 parts of composite filler, 15 parts of high-adsorption kaolin and 5 parts of chitosan;
the sewage treatment adsorbent is prepared by the following method:
adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, carrying out ball milling for 1h at the rotating speed of 450r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
Further, the composite filler is prepared by the following method:
step S1, adding P123 and dilute hydrochloric acid with the concentration of 2mol/L into a three-neck flask, adding deionized water after uniformly mixing, heating to 30 ℃, stirring at a constant speed until P123 is completely dissolved, then dropwise adding ethyl orthosilicate, controlling the dropping speed to be 1 drop/1 second, stirring at a constant speed of 100r/min for 20 hours after the dropping is finished to prepare a reactant, adding the reactant into a reaction kettle with a polytetrafluoroethylene lining, heating to 80 ℃, standing at the temperature for crystallization for 24h, taking out, washing with deionized water for three times, filtering, drying at 45 deg.C for 20 hr to obtain crude product, adding the crude product into an extractor, refluxing acidified ethanol for 24h, then washing the acidified ethanol to be neutral by deionized water, and drying the washed acidified ethanol to obtain an intermediate, wherein the dosage ratio of P123, dilute hydrochloric acid, deionized water and tetraethoxysilane is controlled to be 2 g: 60 mL: 10 mL: 4 g;
s2, activating the intermediate prepared in the step S1 for 6 hours in vacuum at 100 ℃, adding the activated intermediate into anhydrous toluene after activation is finished, dispersing the intermediate at a high speed of 450r/min for 30 minutes, dropwise adding 3-aminopropyltriethoxysilane, continuously dispersing the intermediate for 30 minutes, performing reflux reaction for 2 hours in a nitrogen atmosphere, filtering the mixture, washing the mixture by using a first mixed solution to remove unreacted 3-aminopropyltriethoxysilane, performing reflux for 12 hours by using a Soxhlet extractor with a second mixed solution, performing suction filtration, and performing vacuum drying at 45 ℃ for 10 hours to prepare a modified intermediate, wherein the use ratio of the intermediate to the 3-aminopropyltriethoxysilane is controlled to be 1 g: 1 mL;
step S3, adding 8-hydroxyquinoline and ethanol into a sodium hydroxide aqueous solution with the mass fraction of 45%, dropwise adding chloroform after uniformly mixing, controlling the dropwise adding time to be 10min, refluxing for 10h under a nitrogen atmosphere after dropwise adding, rotationally evaporating unreacted ethanol, chloroform and deionized water after reaction is finished to prepare a reaction product, adding the reaction product into deionized water, dropwise adding 0.1mol/L diluted hydrochloric acid after uniformly stirring for 30min to adjust the pH until the pH is 6, extracting and drying to prepare a second intermediate, and controlling the dosage ratio of 8-hydroxyquinoline, ethanol, the sodium hydroxide aqueous solution and the chloroform to be 25 g: 100 mL: 60 mL: 25 mL;
and step S4, adding the modified intermediate and the second intermediate into a three-neck flask, adding absolute ethyl alcohol, uniformly mixing, heating and refluxing for 10 hours under a nitrogen atmosphere, filtering after the reaction is finished, washing for three times by using the absolute ethyl alcohol, and then drying for 10 hours in vacuum at 50 ℃ to obtain the composite filler, wherein the weight ratio of the modified intermediate to the second intermediate is controlled to be 4: 3.
The first mixed solution is formed by mixing toluene and dichloromethane according to the volume ratio of 1: 1, the second mixed solution is formed by mixing diethyl ether and dichloromethane according to the volume ratio of 1: 1, and the acidified ethanol is formed by mixing hydrochloric acid with the mass fraction of 35% and absolute ethanol according to the volume ratio of 3: 50.
The high adsorption kaolin is prepared by the following method:
uniformly mixing kaolin and potassium acetate according to the weight ratio of 1: 1, adding deionized water for mixing, carrying out mild grinding for 30min, standing for 20h, drying in a water bath kettle at 55 ℃ for 10h to obtain treated kaolin, adding the treated kaolin into a hydrochloric acid solution with the mass fraction of 10%, magnetically stirring at the rotating speed of 120r/min for 20min, carrying out suction filtration, washing with absolute ethyl alcohol for three times, transferring to a drying box at 60 ℃ and drying for 20h to obtain the high-adsorption kaolin.
Example 2
The sewage treatment adsorbent is characterized by comprising the following raw materials in parts by weight: 40 parts of composite filler, 20 parts of high-adsorption kaolin and 8 parts of chitosan;
the sewage treatment adsorbent is prepared by the following method:
adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, carrying out ball milling for 1h at the rotating speed of 450r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
Further, the composite filler is prepared by the following method:
step S1, adding P123 and dilute hydrochloric acid with the concentration of 2mol/L into a three-neck flask, adding deionized water after uniformly mixing, heating to 30 ℃, stirring at constant speed until P123 is completely dissolved, then dropwise adding tetraethoxysilane, controlling the dropping speed to be 1 drop/1 second, stirring at constant speed of 100r/min for 20 hours after the dropping is finished to prepare a reactant, adding the reactant into a reaction kettle with a polytetrafluoroethylene lining, heating to 80 ℃, standing at the temperature for crystallization for 24h, taking out, washing with deionized water for three times, filtering, drying at 45 deg.C for 20 hr to obtain crude product, adding the crude product into an extractor, refluxing acidified ethanol for 24 hours, washing the acidified ethanol to be neutral by using deionized water, and drying the washed ethanol to obtain an intermediate, wherein the using amount ratio of P123, dilute hydrochloric acid, deionized water and tetraethoxysilane is controlled to be 2 g/60 mL/10 mL/4 g;
s2, activating the intermediate prepared in the step S1 for 6 hours in vacuum at 100 ℃, adding the activated intermediate into anhydrous toluene after activation is finished, dispersing the intermediate at a high speed of 450r/min for 30 minutes, dropwise adding 3-aminopropyltriethoxysilane, continuously dispersing the intermediate for 30 minutes, performing reflux reaction for 2 hours in a nitrogen atmosphere, filtering the mixture, washing the mixture by using a first mixed solution to remove unreacted 3-aminopropyltriethoxysilane, performing reflux for 12 hours by using a Soxhlet extractor with a second mixed solution, performing suction filtration, and performing vacuum drying at 45 ℃ for 10 hours to prepare a modified intermediate, wherein the use ratio of the intermediate to the 3-aminopropyltriethoxysilane is controlled to be 1 g: 1 mL;
step S3, adding 8-hydroxyquinoline and ethanol into a sodium hydroxide aqueous solution with the mass fraction of 45%, uniformly mixing, dropwise adding chloroform, controlling the dropwise adding time to be 10min, refluxing for 10h in a nitrogen atmosphere after the dropwise adding is finished, rotationally evaporating unreacted ethanol, chloroform and deionized water after the reaction is finished to obtain a reaction product, adding the reaction product into deionized water, uniformly stirring for 30min, dropwise adding 0.1mol/L dilute hydrochloric acid to adjust the pH until the pH is 6, extracting and drying to obtain a second intermediate, and controlling the dosage ratio of 8-hydroxyquinoline, ethanol, sodium hydroxide aqueous solution and chloroform to be 25 g: 100 mL: 60 mL: 25 mL;
and step S4, adding the modified intermediate and the second intermediate into a three-neck flask, adding absolute ethyl alcohol, uniformly mixing, heating and refluxing for 10 hours under a nitrogen atmosphere, filtering after the reaction is finished, washing for three times by using the absolute ethyl alcohol, and then drying for 10 hours in vacuum at 50 ℃ to obtain the composite filler, wherein the weight ratio of the modified intermediate to the second intermediate is controlled to be 4: 3.
The first mixed solution is formed by mixing toluene and dichloromethane according to the volume ratio of 1: 1, the second mixed solution is formed by mixing diethyl ether and dichloromethane according to the volume ratio of 1: 1, and the acidified ethanol is formed by mixing hydrochloric acid with the mass fraction of 35% and absolute ethanol according to the volume ratio of 3: 50.
The high adsorption kaolin is prepared by the following method:
uniformly mixing kaolin and potassium acetate according to the weight ratio of 1: 1, adding deionized water for mixing, carrying out mild grinding for 30min, standing for 20h, drying in a 55 ℃ water bath for 10h to obtain treated kaolin, adding the treated kaolin into a hydrochloric acid solution with the mass fraction of 10%, magnetically stirring at the rotating speed of 120r/min for 20min, carrying out suction filtration, washing with absolute ethyl alcohol for three times, and transferring to a 60 ℃ drying box for drying for 20h to obtain the high-adsorption kaolin.
Example 3
The sewage treatment adsorbent is characterized by comprising the following raw materials in parts by weight: 45 parts of composite filler, 25 parts of high-adsorption kaolin and 12 parts of chitosan;
the sewage treatment adsorbent is prepared by the following method:
adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, carrying out ball milling for 1h at the rotating speed of 450r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
Further, the composite filler is prepared by the following method:
step S1, adding P123 and dilute hydrochloric acid with the concentration of 2mol/L into a three-neck flask, adding deionized water after uniformly mixing, heating to 30 ℃, stirring at a constant speed until P123 is completely dissolved, then dropwise adding ethyl orthosilicate, controlling the dropping speed to be 1 drop/1 second, stirring at a constant speed of 100r/min for 20 hours after the dropping is finished to prepare a reactant, adding the reactant into a reaction kettle with a polytetrafluoroethylene lining, heating to 80 ℃, standing at the temperature for crystallization for 24h, taking out, washing with deionized water for three times, filtering, drying at 45 deg.C for 20 hr to obtain crude product, adding the crude product into an extractor, refluxing acidified ethanol for 24h, then washing the acidified ethanol to be neutral by deionized water, and drying the washed acidified ethanol to obtain an intermediate, wherein the dosage ratio of P123, dilute hydrochloric acid, deionized water and tetraethoxysilane is controlled to be 2 g: 60 mL: 10 mL: 4 g;
step S2, activating the intermediate prepared in the step S1 for 6 hours in vacuum at 100 ℃, adding the activated intermediate into anhydrous toluene after activation, dispersing the intermediate at a high speed of 450r/min for 30 minutes, dropwise adding 3-aminopropyl triethoxysilane, continuously dispersing the intermediate for 30 minutes, refluxing the intermediate for 2 hours in a nitrogen atmosphere, filtering the mixture, washing the mixture by using a first mixed solution to remove unreacted 3-aminopropyl triethoxysilane, refluxing the mixture by using a Soxhlet extractor for 12 hours by using a second mixed solution, performing suction filtration, and drying the mixture in vacuum at 45 ℃ for 10 hours to prepare a modified intermediate, wherein the using amount ratio of the intermediate to the 3-aminopropyl triethoxysilane is controlled to be 1 g: 1 mL;
step S3, adding 8-hydroxyquinoline and ethanol into a sodium hydroxide aqueous solution with the mass fraction of 45%, dropwise adding chloroform after uniformly mixing, controlling the dropwise adding time to be 10min, refluxing for 10h under a nitrogen atmosphere after dropwise adding, rotationally evaporating unreacted ethanol, chloroform and deionized water after reaction is finished to prepare a reaction product, adding the reaction product into deionized water, dropwise adding 0.1mol/L diluted hydrochloric acid after uniformly stirring for 30min to adjust the pH until the pH is 6, extracting and drying to prepare a second intermediate, and controlling the dosage ratio of 8-hydroxyquinoline, ethanol, the sodium hydroxide aqueous solution and the chloroform to be 25 g: 100 mL: 60 mL: 25 mL;
and step S4, adding the modified intermediate and the second intermediate into a three-neck flask, adding absolute ethyl alcohol, uniformly mixing, heating and refluxing for 10 hours under a nitrogen atmosphere, filtering after the reaction is finished, washing for three times by using the absolute ethyl alcohol, and then drying for 10 hours in vacuum at 50 ℃ to obtain the composite filler, wherein the weight ratio of the modified intermediate to the second intermediate is controlled to be 4: 3.
The first mixed solution is formed by mixing toluene and dichloromethane according to the volume ratio of 1: 1, the second mixed solution is formed by mixing diethyl ether and dichloromethane according to the volume ratio of 1: 1, and the acidified ethanol is formed by mixing hydrochloric acid with the mass fraction of 35% and absolute ethanol according to the volume ratio of 3: 50.
The high adsorption kaolin is prepared by the following method:
uniformly mixing kaolin and potassium acetate according to the weight ratio of 1: 1, adding deionized water for mixing, carrying out mild grinding for 30min, standing for 20h, drying in a 55 ℃ water bath for 10h to obtain treated kaolin, adding the treated kaolin into a hydrochloric acid solution with the mass fraction of 10%, magnetically stirring at the rotating speed of 120r/min for 20min, carrying out suction filtration, washing with absolute ethyl alcohol for three times, and transferring to a 60 ℃ drying box for drying for 20h to obtain the high-adsorption kaolin.
Example 4
The sewage treatment adsorbent is characterized by comprising the following raw materials in parts by weight: 50 parts of composite filler, 30 parts of high-adsorption kaolin and 15 parts of chitosan;
the sewage treatment adsorbent is prepared by the following method:
adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, performing ball milling for 1h at the rotating speed of 450r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
Further, the composite filler is prepared by the following method:
step S1, adding P123 and dilute hydrochloric acid with the concentration of 2mol/L into a three-neck flask, adding deionized water after uniformly mixing, heating to 30 ℃, stirring at constant speed until P123 is completely dissolved, then dropwise adding tetraethoxysilane, controlling the dropping speed to be 1 drop/1 second, stirring at constant speed of 100r/min for 20 hours after the dropping is finished to prepare a reactant, adding the reactant into a reaction kettle with a polytetrafluoroethylene lining, heating to 80 ℃, standing at the temperature for crystallization for 24h, taking out, washing with deionized water for three times, filtering, drying in a drying oven at 45 deg.C for 20 hr to obtain crude product, adding the crude product into an extractor, refluxing acidified ethanol for 24 hours, washing the acidified ethanol to be neutral by using deionized water, and drying the washed ethanol to obtain an intermediate, wherein the using amount ratio of P123, dilute hydrochloric acid, deionized water and tetraethoxysilane is controlled to be 2 g/60 mL/10 mL/4 g;
s2, activating the intermediate prepared in the step S1 for 6 hours in vacuum at 100 ℃, adding the activated intermediate into anhydrous toluene after activation is finished, dispersing the intermediate at a high speed of 450r/min for 30 minutes, dropwise adding 3-aminopropyltriethoxysilane, continuously dispersing the intermediate for 30 minutes, performing reflux reaction for 2 hours in a nitrogen atmosphere, filtering the mixture, washing the mixture by using a first mixed solution to remove unreacted 3-aminopropyltriethoxysilane, performing reflux for 12 hours by using a Soxhlet extractor with a second mixed solution, performing suction filtration, and performing vacuum drying at 45 ℃ for 10 hours to prepare a modified intermediate, wherein the use ratio of the intermediate to the 3-aminopropyltriethoxysilane is controlled to be 1 g: 1 mL;
step S3, adding 8-hydroxyquinoline and ethanol into a sodium hydroxide aqueous solution with the mass fraction of 45%, uniformly mixing, dropwise adding chloroform, controlling the dropwise adding time to be 10min, refluxing for 10h in a nitrogen atmosphere after the dropwise adding is finished, rotationally evaporating unreacted ethanol, chloroform and deionized water after the reaction is finished to obtain a reaction product, adding the reaction product into deionized water, uniformly stirring for 30min, dropwise adding 0.1mol/L dilute hydrochloric acid to adjust the pH until the pH is 6, extracting and drying to obtain a second intermediate, and controlling the dosage ratio of 8-hydroxyquinoline, ethanol, sodium hydroxide aqueous solution and chloroform to be 25 g: 100 mL: 60 mL: 25 mL;
and step S4, adding the modified intermediate and the second intermediate into a three-neck flask, adding absolute ethyl alcohol, uniformly mixing, heating and refluxing for 10 hours under a nitrogen atmosphere, filtering after the reaction is finished, washing for three times by using the absolute ethyl alcohol, and then drying for 10 hours in vacuum at 50 ℃ to obtain the composite filler, wherein the weight ratio of the modified intermediate to the second intermediate is controlled to be 4: 3.
The first mixed solution is formed by mixing toluene and dichloromethane according to the volume ratio of 1: 1, the second mixed solution is formed by mixing diethyl ether and dichloromethane according to the volume ratio of 1: 1, and the acidified ethanol is formed by mixing hydrochloric acid with the mass fraction of 35% and absolute ethanol according to the volume ratio of 3: 50.
The high-adsorption kaolin is prepared by the following method:
uniformly mixing kaolin and potassium acetate according to the weight ratio of 1: 1, adding deionized water for mixing, carrying out mild grinding for 30min, standing for 20h, drying in a 55 ℃ water bath for 10h to obtain treated kaolin, adding the treated kaolin into a hydrochloric acid solution with the mass fraction of 10%, magnetically stirring at the rotating speed of 120r/min for 20min, carrying out suction filtration, washing with absolute ethyl alcohol for three times, and transferring to a 60 ℃ drying box for drying for 20h to obtain the high-adsorption kaolin.
Comparative example 1
Compared with example 1, the preparation method of the comparative example, which replaces the composite filler with the molecular sieve, is as follows:
adding the molecular sieve, the high-adsorption kaolin and the chitosan into a ball mill, carrying out ball milling for 1h at the rotating speed of 450r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
Comparative example 2
In comparison with example 1, the present comparative example was prepared without the addition of highly adsorptive kaolin as follows:
adding the composite filler and chitosan into a ball mill, ball-milling for 1h at the rotating speed of 450r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
Comparative example 3
This comparative example is a commercial activated carbon adsorbent.
The results of examining the treatment rates of the plating wastewater in examples 1 to 4 and comparative examples 1 to 3 are shown in the following tables:
| example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| The treatment rate% | 98 | 97 | 98 | 99 | 65 | 85 | 70 |
As can be seen from the above table, the treatment rates of examples 1 to 4 were 97 to 99%, and the treatment rates of comparative examples 1 to 3 were 65 to 85%; therefore, 8-hydroxyquinoline, ethanol, trichloromethane and sodium hydroxide are mixed to prepare a second intermediate, the second intermediate is an 8-hydroxyquinoline derivative, then the modified intermediate and the second intermediate are mixed in absolute ethanol in step S4, the second intermediate is grafted on the inner surface of the modified intermediate, and the 8-hydroxyquinoline derivative has excellent antibacterial performance and endows the finally prepared composite filler with metal chelation and antibacterial performance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (4)
1. The sewage treatment adsorbent is characterized by comprising the following raw materials in parts by weight: 35-50 parts of composite filler, 15-30 parts of high-adsorption kaolin and 5-15 parts of chitosan;
the sewage treatment adsorbent is prepared by the following method:
adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, carrying out ball milling for 1h at the rotating speed of 1500-2000r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent;
the composite filler is prepared by the following method:
step S1, adding P123 and dilute hydrochloric acid with the concentration of 2mol/L into a three-neck flask, adding deionized water after uniform mixing, heating to 30-40 ℃, stirring at constant speed until P123 is completely dissolved, then dropwise adding tetraethoxysilane, controlling the dropping speed to be 1 drop/1 second, stirring at constant speed of 100 plus 200r/min for 20 hours after the dropping is finished to obtain a reactant, adding the reactant into a reaction kettle with a polytetrafluoroethylene lining, heating to 80-100 ℃, standing at the temperature for crystallization for 24h, taking out, washing with deionized water for three times, filtering, drying in a drying oven at 45-60 deg.C for 20 hr to obtain crude product, adding the crude product into an extractor, refluxing acidified ethanol for 24h, then washing the acidified ethanol to be neutral by deionized water, and drying the washed acidified ethanol to obtain an intermediate, wherein the dosage ratio of P123, dilute hydrochloric acid, deionized water and tetraethoxysilane is controlled to be 2 g: 60 mL: 8-10 mL: 4 g;
s2, activating the intermediate prepared in the step S1 for 6 hours in vacuum at the temperature of 100-120 ℃, adding the activated intermediate into anhydrous toluene, dispersing the intermediate for 30 minutes at a high speed of 500r/min at the speed of 450-500r/min, dropwise adding 3-aminopropyltriethoxysilane, continuously dispersing the intermediate for 30 minutes, refluxing the intermediate for 2 hours in a nitrogen atmosphere, filtering the mixture, washing the mixture by using a first mixed solution to remove unreacted 3-aminopropyltriethoxysilane, refluxing the mixture for 12 hours by using a Soxhlet extractor by using a second mixed solution, performing suction filtration, and drying the mixture for 10 hours in vacuum at the temperature of 45-60 ℃ to prepare a modified intermediate, wherein the use ratio of the intermediate to the 3-aminopropyltriethoxysilane is controlled to be 1 g: 1 mL;
step S3, adding 8-hydroxyquinoline and ethanol into a sodium hydroxide aqueous solution with the mass fraction of 45%, dropwise adding chloroform after uniformly mixing, controlling the dropwise adding time to be 10min, refluxing for 10h under a nitrogen atmosphere after dropwise adding, rotationally evaporating unreacted ethanol, chloroform and deionized water after reaction is finished to prepare a reaction product, adding the reaction product into deionized water, dropwise adding 0.1mol/L diluted hydrochloric acid after uniformly stirring for 30min to adjust the pH until the pH is 6-6.5, extracting and drying to prepare a second intermediate, and controlling the dosage ratio of 8-hydroxyquinoline, ethanol, the sodium hydroxide aqueous solution and the chloroform to be 25 g: 100 mL: 60 mL: 25 mL;
and step S4, adding the modified intermediate and the second intermediate into a three-neck flask, adding absolute ethyl alcohol, uniformly mixing, heating and refluxing for 10 hours under a nitrogen atmosphere, filtering after the reaction is finished, washing for three times by using the absolute ethyl alcohol, and drying for 10 hours in vacuum at 50-80 ℃ to obtain the composite filler, wherein the weight ratio of the modified intermediate to the second intermediate is controlled to be 4: 3.
2. The sewage treatment adsorbent according to claim 1, wherein the first mixed solution is formed by mixing toluene and dichloromethane at a volume ratio of 1: 1, the second mixed solution is formed by mixing diethyl ether and dichloromethane at a volume ratio of 1: 1, and the acidified ethanol is formed by mixing hydrochloric acid with a mass fraction of 35% and absolute ethanol at a volume ratio of 3: 50.
3. The sewage treatment adsorbent according to claim 1, wherein the highly adsorbent kaolin is prepared by the following method:
uniformly mixing kaolin and potassium acetate according to the weight ratio of 1: 1, adding deionized water for mixing, carrying out mild grinding for 30min, standing for 20h, drying in a water bath kettle at 55-60 ℃ for 10h to obtain treated kaolin, adding the treated kaolin into a hydrochloric acid solution with the mass fraction of 10%, magnetically stirring at the rotating speed of 120r/min for 20min, carrying out suction filtration, washing with absolute ethyl alcohol for three times, and transferring to a drying box at 55-60 ℃ for drying for 20h to obtain the high-adsorption kaolin.
4. The preparation method of the sewage treatment adsorbent according to claim 1, comprising the steps of:
adding the composite filler, the high-adsorption kaolin and the chitosan into a ball mill, ball-milling for 1h at the rotating speed of 450-plus-one 500r/min to prepare a mixture, adding the mixture into a cylindrical granulator, and granulating to prepare the sewage treatment adsorbent.
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