CN114643048A - Composite adsorption material and preparation method and application thereof - Google Patents

Composite adsorption material and preparation method and application thereof Download PDF

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CN114643048A
CN114643048A CN202210316998.0A CN202210316998A CN114643048A CN 114643048 A CN114643048 A CN 114643048A CN 202210316998 A CN202210316998 A CN 202210316998A CN 114643048 A CN114643048 A CN 114643048A
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attapulgite
solution
composite
humic acid
dissolving
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刘庆
沈彬
李承前
石羽煣
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Southeast University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • 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

Abstract

The invention discloses a composite adsorbing material and a preparation method and application thereof. The composite adsorption material has excellent adsorption performance, can keep good mechanical performance in an alkaline or neutral environment, is not easy to deform, is easy to recover, effectively solves the problem that humic acid is very soluble in the neutral or alkaline environment, enlarges the application range of the adsorbent, has low cost, and effectively improves the defects of secondary pollution, high price, poor recovery and the like of the traditional adsorbent. Meanwhile, a new idea is provided for the treatment of the municipal wastewater and sludge.

Description

Composite adsorption material and preparation method and application thereof
Technical Field
The invention relates to a composite adsorption material and a preparation method and application thereof, in particular to a natural active high molecular polymer and natural clay composite adsorption material which has an adsorption effect and is purified from municipal sludge, a preparation method and application thereof, and belongs to the technical field of organic materials.
Background
With the rapid development of industry, a large amount of industrial wastewater is discharged into rivers, causing environmental pollution. Heavy metals in industrial wastewater have hard degradability and high toxicity, can be accumulated in organisms, and cause harm to human bodies along with circulation of food chains, the current common water treatment methods comprise a precipitation method, an ion exchange method, a biological treatment method, a membrane separation method and the like, and an adsorption method is widely applied due to low cost, simple equipment, easy operation and environmental friendliness.
Due to its large specific surface area and strong cation exchange capacity, and due to homotypic displacement in the crystal lattice, a large amount of negative charges are present on its surface, so that the attapulgite can effectively remove heavy metal ions and cationic organic pollutants, but the attapulgite is non-selective for adsorption of these pollutants. Cations such as sodium ions, calcium ions, etc., which are commonly found in water, are also adsorbed onto the surface of the attapulgite. The existence of competitive adsorption can affect the adsorption effect of the attapulgite on heavy metal ions and cationic organic pollutants. Moreover, because the surface of the attapulgite is provided with a plurality of negative charges, the existence of electrostatic repulsion makes anionic pollutants difficult to be adsorbed on the attapulgite. The natural attapulgite has carbonate cement in the interlayer and some adsorbed cations on the surface, so that the adsorption capacity of the natural attapulgite on pollutants is relatively low. For the reasons, natural attapulgite often needs to be modified to effectively remove heavy metal ions in water.
The source of humus includes, besides remains of animals and plants, sludge and the like, which are organic matter with natural activity formed by the action of microorganisms and a series of physicochemical processes into multifunctional amorphous masses with high molecular structures and colloidal properties. Humic acid contains various functional groups and presents the characteristics of a surfactant, so that the humic acid has the capability of enhancing ion exchange and complexing heavy metals, but is very easy to dissolve in water and influenced by pH, and is generally modified in order to solve the problem of the solubility of the humic acid and achieve various use purposes. A modification method is to fix humic acid on clay or organic and inorganic modified clay, because most of the clay is charged, the clay is charged positively after organic or inorganic modification, and the humic acid is charged negatively, so that the humic acid can react with the modified clay through electrostatic attraction to generate a humic acid-clay compound, and the humic acid is attached to the surface and the inner gaps of the clay, thereby improving the hydrophobicity of the clay. Meanwhile, the existence of humic acid also changes the charge on the surface of the clay, so that the clay has stronger removal capability on metal ions.
In conclusion, the research on a new water treatment material which has good adsorption performance, low price and easy regeneration and is harmful to the health of people and animals and is caused by the pollution of the environment by the uranium-containing wastewater becomes a hotspot of the current research. However, the relatively high price of the adsorbent is a major reason for restricting its application. The humic acid and attapulgite in China have rich resources, wide sources and low cost, and the modified attapulgite has the advantages of large specific surface area, good adsorption performance and the like, is used for removing uranium in wastewater, and has great environmental, social and economic benefits.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems in the prior art, the first purpose of the invention is to provide a composite adsorbing material of humic acid attapulgite which has an adsorption effect and is purified from municipal sludge, the second purpose of the invention is to provide a preparation method of the composite adsorbing material, and the third purpose of the invention is to provide application of the composite adsorbing material in adsorbing uranium-containing wastewater.
The technical scheme is as follows: the composite adsorbing material is prepared by taking attapulgite as a matrix, wherein humic acid is covered on the surface of the attapulgite; the humic acid is obtained by dewatering and curing after being extracted from sludge, and the attapulgite is obtained by modifying with CTAB.
The preparation method of the composite adsorption material comprises the following steps:
dissolving sludge in a sodium hydroxide solution, stirring for reaction, filtering to obtain a solution, adjusting the pH value of the solution, and performing centrifugal separation for multiple times to obtain a centrifugal product;
(2) calcining the centrifugal product, soaking in calcium chloride solution, filtering, soaking in sodium nitrate solution, suction filtering, repeatedly washing with nitric acid solution and water, and drying to obtain humic acid;
(3) adding attapulgite into a dilute sulfuric acid solution, stirring for reaction, performing suction filtration, washing, calcining, crushing, and sieving to obtain acidified attapulgite;
(4) dissolving Cetyl Trimethyl Ammonium Bromide (CTAB) in absolute ethyl alcohol, adding acidified attapulgite, performing ultrasonic reaction at normal temperature, performing suction filtration, washing, calcining, crushing and sieving to obtain CTAB modified attapulgite;
(5) dissolving humic acid in NaOH solution, adding CTAB modified attapulgite, stirring for dissolving, and adjusting pH value to obtain a mixture;
(6) and oscillating the mixture for reaction, performing centrifugal separation, washing with water for multiple times, drying, and grinding to obtain the composite adsorbing material (HA/ATP).
In the step (1), the solid-to-liquid ratio of the sludge to the sodium hydroxide solution is 1:10-1:12g/mL, and the centrifugal separation times are 3-5.
Wherein in the step (2), the calcining temperature is 300-400 ℃, the calcining time is 1-3h, the concentration of the calcium chloride solution is 2-3mol/L, and the concentration of the sodium nitrate solution is 1-1.5 mol/L.
In the step (3), the solid-to-liquid ratio of the attapulgite to the dilute sulfuric acid solution is 1:10-1:12g/mL, and the volume concentration of the dilute sulfuric acid solution is 10-20%.
In the step (4), the solid-to-liquid ratio of the hexadecyl trimethyl ammonium bromide to the absolute ethyl alcohol is 1:100-1:150g/mL, and the mass ratio of the acidified attapulgite to the hexadecyl trimethyl ammonium bromide is 1:8-1: 12.
In the step (5), the mass ratio of the humic acid to the CTAB modified attapulgite is 1:4-3:2, and the pH value is adjusted to 1-6.
Wherein, in the step (6), the oscillation reaction time is 15-20 h.
Wherein, the structure model of humic acid Stevenson is as follows:
Figure BDA0003570095060000031
the basic structure of the attapulgite is shown in fig. 1.
The invention also comprises the application of the composite adsorbing material in adsorbing uranium-containing wastewater.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the composite adsorbing material prepared by the invention has excellent adsorption performance, and in an SEM picture, the composite adsorbing material has a rough surface, a loose structure, a plurality of apertures and holes with different sizes and shapes, which is beneficial to adsorbing pollutants by the composite.
(2) The composite adsorption material obtained by the invention can keep good mechanical property in alkaline or neutral environment, the adsorbent is not easy to deform and easy to recover, the problem that humic acid is very soluble in neutral or alkaline environment is effectively solved, and the application range of the adsorbent is expanded.
(3) The composite adsorbing material prepared by the invention adopts natural attapulgite clay as the main component of the adsorbent, and the active high molecular polymer humic acid extracted and purified from sludge is used for modifying the adsorbent, so that the cost is low, and the defects of secondary pollution, high price, poor recovery and the like of the traditional adsorbent are effectively overcome.
(4) The method provides a new idea for the treatment of the municipal wastewater and sludge.
Drawings
FIG. 1 is a basic structural view of attapulgite;
FIG. 2 is an SEM image of attapulgite and a composite adsorbent material;
FIG. 3 is an XRD pattern of attapulgite and composite adsorbent material;
fig. 4 is a diagram of uranium adsorption effect of attapulgite and a composite adsorption material.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
1. Humic acid extraction and modification
(1) Weighing 10g of sludge (the sludge in a secondary sedimentation tank of a sewage treatment plant in the main urban area of Nanjing, the average water content of the sludge in the secondary sedimentation tank is 99.5 percent) and dissolving the sludge in 100ml of 0.1mol/L sodium hydroxide solution for reaction for 2 hours, and filtering out undissolved impurities;
(2) adjusting the pH value of the solution to 1 by 6mo1/L HC1 solution, placing the solution in a water bath oscillation box at 65 ℃, setting t to 2h and n to 150r/min, and repeatedly centrifuging for 3 times to obtain a centrifugal product;
(3) placing the centrifugal product in a muffle furnace at 300 ℃, and burning for 1h to rapidly dehydrate the centrifugal product to obtain a burning product;
(4) and (3) soaking the burned product in 2mol/L calcium chloride solution for 2h, filtering, soaking the precipitate in 1.5mol/L sodium nitrate solution for 30min, performing suction filtration, repeatedly washing with 1mol/L nitric acid solution and distilled water, and drying and storing the obtained solid to obtain the humic acid.
2. Attapulgite modification
(1) Adding 10g of attapulgite into 100ml of a 15% dilute sulfuric acid solution, reacting for 2 hours under magnetic stirring, and cooling and filtering after the reaction is finished to obtain a filter cake;
(2) washing the filter cake to be neutral by using deionized water, roasting the washed filter cake in a muffle furnace at 350 ℃ for 2h, crushing, and sieving by using a 180-mesh sieve to obtain acidified attapulgite;
(3) dissolving 0.6g of hexadecyl trimethyl ammonium bromide (CTAB) in 60ml of absolute ethyl alcohol, adding 6g of acidified attapulgite, and performing ultrasonic modification at normal temperature for 2 hours;
(4) filtering, washing the precipitate until no bromide ion (using 0.01mol/L AgNO)3Detection), roasting for 2h at 110 ℃ in a muffle furnace, crushing, and sieving with a 180-mesh sieve to obtain the CTAB modified attapulgite.
3. Preparation of composite adsorption material
(1) Dissolving 6g of humic acid in 0.1mol/L NaOH solution to obtain NaOH solution of humic acid;
(2) adding 6g of CTAB modified attapulgite into a NaOH solution of humic acid, and adjusting the pH value of the solution to 2 after dissolving to obtain a mixture;
(3) putting the mixture into a shaking incubator, setting the temperature T to be 35 ℃, setting the temperature n to be 150r/min, and carrying out shaking reaction for 16 h;
(4) and after the vibration is finished, performing centrifugal separation, collecting the precipitate, washing the precipitate for multiple times by using distilled water, and drying and grinding the washed precipitate in a 65-DEG C oven to obtain the composite adsorbing material.
4. Scanning electron microscope testing of attapulgite and composite adsorbent materials
Fully dried ATP and HA/ATP are respectively placed on polished aluminum sheets, gold spraying is carried out to prepare an electron microscope sample, and the sample microstructure is observed by adopting an FEI Quanta-200 type environment scanning electron microscope (USA).
As a result, as shown in fig. 2, fig. 2 is an SEM image of the attapulgite and the composite adsorbent, wherein (a) is attapulgite ATP and (b) is the composite adsorbent HA/ATP. As can be seen from fig. 2, the surface of the attapulgite in (a) is uneven, and many voids and cavities are distributed. (b) After the attapulgite is modified by the medium humic acid, the surface morphology is changed, the gaps and the cavities on the surface are increased, and a layer of dark substance is covered, which shows that a certain amount of humic acid is bonded on the attapulgite, and the preparation of the composite adsorbing material is successful.
5. X-ray diffraction test of attapulgite and composite adsorbing material
Analyzing the phases of the attapulgite and the composite adsorption material sample by using a D/max 2500PC type powder X-ray diffractometer (X-ray diffraction, XRD), wherein the testing temperature is room temperature, and a Cu target K is adoptedαRadiation (λ 0.15406nm) at scan angles ranging from 3 ° to 70 °.
As a result, as shown in fig. 3, fig. 3 is an XRD chart of the attapulgite and the composite adsorbent, in which (a) is the attapulgite and (b) is the composite adsorbent. As can be seen from fig. 3, the main diffraction peak of the composite adsorbing material of humic acid attapulgite is consistent with that of attapulgite, which indicates that the crystal structure of attapulgite is not changed after humic acid modification, and humic acid mainly modifies the surface of attapulgite.
6. Test of uranium adsorption effect of attapulgite and composite adsorption material
In the wastewater with the mass concentration of uranium solution of 30mg/L, the temperature is 25 ℃, the pH is 6, and the volume of the solution is 50mL, the adding amount of HA/ATP is adjusted to be 25mg, 35mg, 50mg, 100mg, 150mg, 200mg, 250mg, 300mg and 350mg respectively, centrifugal filtration is carried out after adsorption reaction is carried out for 1h, the mass concentration of residual uranium is measured by taking the filtrate, and the influence of the adding amount of HA/ATP on the uranium adsorption effect is researched.
As a result, as shown in fig. 4, fig. 4 is a graph showing the uranium adsorption effect of the attapulgite and the composite adsorbent, and it can be seen from fig. 4 that the removal rate gradually increases with the increase of the addition amount, and the removal rate becomes maximum when the addition amount is 4 mg/mL. Compared with natural attapulgite clay (ATP) without surface modification, the composite adsorbing material (HA/ATP) prepared by treating the attapulgite clay with humic acid HAs a remarkably improved uranium adsorbing effect. The method is probably caused by the existence of humic acid, on one hand, HA increases the electronegativity of ATP, and on the other hand, HA contains a large number of functional groups such as phenolic hydroxyl groups and carboxyl groups which can be complexed with heavy metals, so that the HA is widely applied to the aspect of heavy metal adsorption.
Example 2
1. Purification and modification of humic acid
(1) Weighing 5g of sludge, dissolving the sludge in 60ml of 0.1mol/L sodium hydroxide solution, reacting for 2 hours, and filtering undissolved impurities;
(2) adjusting the pH value of the solution to 1 by 6mo1/L HC1 solution, placing the solution in a water bath oscillation box at 65 ℃, setting t to 2h and n to 150r/min, and repeatedly centrifuging for 5 times to obtain a centrifugal product;
(3) placing the centrifugal product in a muffle furnace at 350 ℃, and firing for 1h to rapidly dehydrate the centrifugal product to obtain a firing product;
(4) and (3) soaking the burned product in 2.5mol/L calcium chloride solution for 2h, filtering, soaking the precipitate in 1mol/L sodium nitrate solution for 30min, performing suction filtration, repeatedly washing with 1mol/L nitric acid solution and distilled water, and drying and storing the obtained solid to obtain the humic acid.
2. Attapulgite modification
(1) Adding 10g of attapulgite into 120ml of 10% dilute sulfuric acid solution, reacting for 2 hours by magnetic stirring, fully reacting, cooling and filtering after the reaction is finished, and obtaining a filter cake;
(2) washing the filter cake to be neutral by using deionized water, roasting the washed filter cake in a muffle furnace at 350 ℃ for 2h, crushing, and sieving by using a 180-mesh sieve to obtain acidified attapulgite;
(3) dissolving 0.8g of hexadecyl trimethyl ammonium bromide (CTAB) in 80ml of absolute ethyl alcohol, adding 6.4g of acidified attapulgite, and performing ultrasonic modification at normal temperature for 2 hours;
(4) and (3) carrying out suction filtration, washing the precipitate until no bromide ions exist (detected by 0.01mol/L AgNO 3), roasting for 2h at 110 ℃ in a muffle furnace, crushing, and sieving with a 180-mesh sieve to obtain the CTAB modified attapulgite.
3. Preparation of composite adsorption material
(1) Dissolving 0.25g of humic acid in 0.1mol/L NaOH solution to obtain NaOH solution of humic acid;
(2) adding 1g of CTAB modified attapulgite into a humic acid NaOH solution, and adjusting the pH value of the solution to 3 after dissolving to obtain a mixture;
(3) putting the mixture into a shaking incubator, setting the temperature T to be 35 ℃, setting the temperature n to be 150r/min, and carrying out shaking reaction for 20 h;
(4) and after the vibration is finished, performing centrifugal separation, collecting the precipitate, washing the precipitate for multiple times by using distilled water, and drying and grinding the washed precipitate in a 65-DEG C oven to obtain the composite adsorbing material.
Example 3
1. Purification and modification of humic acid
(1) Weighing 20g of sludge, dissolving the sludge in 200ml of 0.1mol/L sodium hydroxide solution, reacting for 2 hours, and filtering undissolved impurities;
(2) adjusting the pH value of the solution to 1 by 6mo1/L HC1 solution, placing the solution in a water bath oscillation box at 65 ℃, setting t to 2h and n to 150r/min, and repeatedly centrifuging for 4 times to obtain a centrifugal product;
(3) placing the centrifugal product in a 400 ℃ muffle furnace, and firing for 3h to rapidly dehydrate the centrifugal product to obtain a firing product;
(4) and (3) soaking the burned product in 3mol/L calcium chloride solution for 2h, filtering, soaking the precipitate in 2mol/L sodium nitrate solution for 30min, performing suction filtration, repeatedly washing with 1mol/L nitric acid solution and distilled water, and drying and storing the obtained solid to obtain the humic acid.
2. Attapulgite modification
(1) Adding 13g of attapulgite into 130ml of 12% dilute sulfuric acid solution, carrying out magnetic stirring reaction for 2 hours to ensure that the attapulgite and the 12% dilute sulfuric acid solution react fully, and cooling and carrying out suction filtration after the reaction is finished to obtain a filter cake;
(2) washing the filter cake to be neutral by using deionized water, roasting the washed filter cake in a muffle furnace at 350 ℃ for 2h, crushing, and sieving by using a 180-mesh sieve to obtain acidified attapulgite;
(3) dissolving 1g of Cetyl Trimethyl Ammonium Bromide (CTAB) in 100ml of absolute ethyl alcohol, adding 10g of acidified attapulgite, and performing ultrasonic modification at normal temperature for 2 hours;
(4) and (3) carrying out suction filtration, washing the precipitate until no bromide ions exist (detected by 0.01mol/L AgNO 3), roasting for 2h in a muffle furnace at 110 ℃, crushing, and sieving with a 180-mesh sieve to obtain the CTAB modified attapulgite.
3. Preparation of composite adsorption material
(1) Dissolving 1.5g of humic acid solid in 0.1mol/L NaOH solution to obtain NaOH solution of humic acid;
(2) adding 1g of CTAB modified attapulgite solid powder into a humic acid NaOH solution, and adjusting the pH value of the solution to 6 after dissolving to obtain a mixture;
(3) putting the mixture into a shaking incubator, setting the temperature T to be 35 ℃, setting the temperature n to be 150r/min, and carrying out shaking reaction for 17 h;
(4) and after the vibration is finished, performing centrifugal separation, collecting the precipitate, washing the precipitate for multiple times by using distilled water, and drying and grinding the washed precipitate in a 65-DEG C oven to obtain the composite adsorbing material.
Example 4
1. Purification and modification of humic acid
(1) Weighing 8g of sludge, dissolving the sludge in 96ml of 0.1mol/L sodium hydroxide solution, reacting for 2 hours, and filtering undissolved impurities;
(2) adjusting the pH value of the solution to 1 by 6mo1/L HC1 solution, placing the solution in a water bath oscillation box at 65 ℃, setting t to 2h and n to 150r/min, and repeatedly centrifuging for 5 times to obtain a centrifugal product;
(3) placing the centrifugal product in a muffle furnace at 320 ℃, and firing for 1h to rapidly dehydrate the centrifugal product to obtain a firing product;
(4) and (3) soaking the burned product in 2.2mol/L calcium chloride solution for 2h, filtering, soaking the precipitate in 1.3mol/L sodium nitrate solution for 30min, performing suction filtration, repeatedly washing with 1mol/L nitric acid solution and distilled water, and drying and storing the obtained solid to obtain the humic acid.
2. Attapulgite modification
(1) Adding 20g of attapulgite into 200ml of 15% dilute sulfuric acid solution, carrying out magnetic stirring reaction for 2 hours to ensure that the attapulgite and the 15% dilute sulfuric acid solution react fully, and cooling and carrying out suction filtration after the reaction is finished to obtain a filter cake;
(2) washing the filter cake to be neutral by using deionized water, roasting the washed filter cake in a muffle furnace at 350 ℃ for 2h, crushing, and sieving by using a 180-mesh sieve to obtain acidified attapulgite;
(3) dissolving 0.9g of hexadecyl trimethyl ammonium bromide (CTAB) in 90ml of absolute ethyl alcohol, adding 9g of acidified attapulgite, and performing ultrasonic modification at normal temperature for 2 hours;
(4) and (3) carrying out suction filtration, washing the precipitate until no bromide ions exist (detected by 0.01mol/L AgNO 3), roasting for 2h in a muffle furnace at 110 ℃, crushing, and sieving with a 180-mesh sieve to obtain the CTAB modified attapulgite.
3. Preparation of composite adsorption material
(1) Dissolving 0.9g of the humic acid solid in 0.1mol/L NaOH solution to obtain NaOH solution of humic acid;
(2) adding 2g of CTAB modified attapulgite solid powder into a humic acid NaOH solution, and adjusting the pH value of the solution to 1 after dissolving to obtain a mixture;
(3) putting the mixture into a shaking incubator, setting the temperature T to be 35 ℃, setting the temperature n to be 150r/min, and carrying out shaking reaction for 18 h;
(4) and after the vibration is finished, performing centrifugal separation, collecting the precipitate, washing the precipitate for multiple times by using distilled water, and drying and grinding the washed precipitate in a 65-DEG C oven to obtain the composite adsorbing material.
Example 5
1. Purification and modification of humic acid
(1) Weighing 30g of sludge, dissolving the sludge in 360ml of 0.1mol/L sodium hydroxide solution, reacting for 2 hours, and filtering undissolved impurities;
(2) adjusting the pH value of the solution to 1 by 6mo1/L HC1 solution, placing the solution in a water bath oscillation box at 65 ℃, setting t to 2h and n to 150r/min, and repeatedly centrifuging for 3 times to obtain a centrifugal product;
(3) placing the centrifugal product in a muffle furnace at 330 ℃, and burning for 1h to quickly dehydrate the centrifugal product to obtain a burning product;
(4) and (3) soaking the burned product in 2.3mol/L calcium chloride solution for 2h, filtering, soaking the precipitate in 1.4mol/L sodium nitrate solution for 30min, performing suction filtration, repeatedly washing with 1mol/L nitric acid solution and distilled water, and drying and storing the obtained solid to obtain the humic acid.
2. Attapulgite modification
(1) Adding 30g of attapulgite into 300ml of 19% dilute sulfuric acid solution, reacting for 2 hours by magnetic stirring, fully reacting, cooling and filtering after the reaction is finished, and obtaining a filter cake;
(2) washing the filter cake to be neutral by using deionized water, roasting the washed filter cake in a muffle furnace at 350 ℃ for 2h, crushing, and sieving by using a 180-mesh sieve to obtain acidified attapulgite;
(3) dissolving 1.2g of hexadecyl trimethyl ammonium bromide (CTAB) in 180ml of absolute ethyl alcohol, adding 14.4g of acidified attapulgite, and performing ultrasonic modification at normal temperature for 2 hours;
(4) and (3) carrying out suction filtration, washing the precipitate until no bromide ions exist (detected by 0.01mol/L AgNO 3), roasting for 2h in a muffle furnace at 110 ℃, crushing, and sieving with a 180-mesh sieve to obtain the CTAB modified attapulgite.
3. Preparation of composite adsorption material
(1) Dissolving 10g of the humic acid solid in 0.1mol/L NaOH solution to obtain NaOH solution of humic acid;
(2) adding 12g of CTAB modified attapulgite solid powder into a humic acid NaOH solution, and adjusting the pH value of the solution to 4 after dissolving to obtain a mixture;
(3) putting the mixture into a shaking incubator, setting the temperature T to be 35 ℃, setting the temperature n to be 150r/min, and carrying out shaking reaction for 20 h;
(4) and after the vibration is finished, performing centrifugal separation, collecting the precipitate, washing the precipitate for multiple times by using distilled water, and drying and grinding the washed precipitate in a 65-DEG C oven to obtain the composite adsorbing material.
Example 6
1. Purification and modification of humic acid
(1) Weighing 15g of sludge, dissolving the sludge in 150ml of 0.1mol/L sodium hydroxide solution, reacting for 2 hours, and filtering undissolved impurities;
(2) adjusting the pH value of the solution to 1 by 6mo1/L HC1 solution, placing the solution in a water bath oscillation box at 65 ℃, setting t to 2h and n to 150r/min, and repeatedly centrifuging for 5 times to obtain a centrifugal product;
(3) placing the centrifugal product in a muffle furnace, and firing for 1h to rapidly dehydrate the centrifugal product to obtain a firing product;
(4) and (3) soaking the burned product in a calcium chloride solution for 2 hours, filtering, soaking the precipitate in a 1.4mol/L sodium nitrate solution for 30 minutes, carrying out suction filtration, repeatedly washing the precipitate with a 1mol/L nitric acid solution and distilled water, and drying and storing the obtained solid to obtain the humic acid.
2. Attapulgite modification
(1) Adding 150g of attapulgite into 1500ml of 20% dilute sulfuric acid solution, carrying out magnetic stirring reaction for 2 hours to ensure that the attapulgite and the sulfuric acid react fully, and cooling and filtering after the reaction is finished to obtain a filter cake;
(2) washing the filter cake to be neutral by using deionized water, roasting the washed filter cake in a muffle furnace at 350 ℃ for 2h, crushing, and sieving by using a 180-mesh sieve to obtain acidified attapulgite;
(3) dissolving 10g of hexadecyl trimethyl ammonium bromide (CTAB) in 1000ml of absolute ethyl alcohol, adding 100g of acidified attapulgite, and carrying out ultrasonic modification at normal temperature for 2 h;
(4) and (3) carrying out suction filtration, washing the precipitate until no bromide ions exist (detected by 0.01mol/L AgNO 3), roasting for 2h in a muffle furnace at 110 ℃, crushing, and sieving with a 180-mesh sieve to obtain the CTAB modified attapulgite.
3. Preparation of composite adsorption material
(1) 5g of humic acid solid is dissolved in 0.1mol/L NaOH solution to obtain NaOH solution of humic acid;
(2) adding 5g of CTAB modified attapulgite solid powder into a humic acid NaOH solution, and adjusting the pH value of the solution to 5 after dissolving to obtain a mixture;
(3) putting the mixture into a shaking incubator, setting the temperature T to be 35 ℃, setting the temperature n to be 150r/min, and carrying out shaking reaction for 15 h;
(4) and after the vibration is finished, performing centrifugal separation, collecting the precipitate, washing the precipitate for multiple times by using distilled water, and drying and grinding the washed precipitate in a 65-DEG C oven to obtain the composite adsorbing material.

Claims (9)

1. The composite adsorption material is characterized in that attapulgite is used as a matrix, and humic acid is covered on the surface of the attapulgite; the humic acid is obtained by dewatering and curing after being extracted from sludge, and the attapulgite is obtained by modifying with CTAB.
2. A method of preparing the composite adsorbent material of claim 1, comprising the steps of:
(1) dissolving sludge in a sodium hydroxide solution, stirring for reaction, filtering to obtain a solution, adjusting the pH value of the solution, and performing centrifugal separation for multiple times to obtain a centrifugal product;
(2) calcining the centrifugal product, soaking in calcium chloride solution, filtering, soaking in sodium nitrate solution, suction filtering, repeatedly washing with nitric acid solution and water, and drying to obtain humic acid;
(3) adding attapulgite into a dilute sulfuric acid solution, stirring for reaction, performing suction filtration, washing, calcining, crushing, and sieving to obtain acidified attapulgite;
(4) dissolving cetyl trimethyl ammonium bromide in absolute ethyl alcohol, adding acidified attapulgite, performing ultrasonic reaction at normal temperature, performing suction filtration, washing, calcining, crushing, and sieving to obtain CTAB modified attapulgite;
(5) dissolving humic acid in NaOH solution, adding CTAB modified attapulgite, stirring for dissolving, and adjusting pH value to obtain a mixture;
(6) and (3) oscillating the mixture for reaction, performing centrifugal separation, washing with water for multiple times, drying, and grinding to obtain the composite adsorbing material.
3. The preparation method of the composite adsorbing material according to claim 2, wherein in the step (1), the solid-to-liquid ratio of the sludge to the sodium hydroxide solution is 1:10-1:12g/mL, and the number of times of centrifugal separation is 3-5.
4. The preparation method of the composite adsorption material according to claim 2, wherein in the step (2), the calcination temperature is 300-.
5. The preparation method of the composite adsorbing material according to claim 2, wherein in the step (3), the solid-to-liquid ratio of the attapulgite to the dilute sulfuric acid solution is 1:10-1:12g/mL, and the volume concentration of the dilute sulfuric acid solution is 10-20%.
6. The preparation method of the composite adsorption material according to claim 2, wherein in the step (4), the solid-to-liquid ratio of the cetyl trimethyl ammonium bromide to the absolute ethyl alcohol is 1:100-1:150g/mL, and the mass ratio of the cetyl trimethyl ammonium bromide to the acidified attapulgite is 1:8-1: 12.
7. The method for preparing the composite adsorbent according to claim 2, wherein in the step (5), the mass ratio of the humic acid to the CTAB-modified attapulgite is 1:4 to 3:2, and the pH value is adjusted to 1 to 6.
8. The method for preparing the composite adsorption material according to claim 2, wherein in the step (6), the oscillation reaction time is 15 to 20 hours.
9. Use of the composite adsorbent material according to claim 1 for adsorbing uranium-containing wastewater.
CN202210316998.0A 2022-03-29 2022-03-29 Composite adsorption material and preparation method and application thereof Pending CN114643048A (en)

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CN103611494A (en) * 2013-11-21 2014-03-05 陕西科技大学 Amido modified attapulgite clay adsorbent and method for preparing and adsorbing humic acid
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