CN114192104B - Adsorbent for adsorbing chromium, preparation method and adsorption method - Google Patents
Adsorbent for adsorbing chromium, preparation method and adsorption method 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
- B01J20/02—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
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention belongs to the technical field of adsorption separation of heavy metals, and relates to an adsorbent for adsorbing chromium, a preparation method and an adsorption method. The adsorbent is amino-functionalized mesoporous silica nano particles, is environment-friendly, simple and convenient in synthesis process, excellent in adsorption performance, and good in stability and environmental adaptability. The adsorbent has good adsorption separation effect on Cr (VI), can realize separation between Cr (VI) and other heavy metals, and has the adsorption removal rate of Cr (VI) reaching 98% and the adsorption removal rate of other metals being less than 10% in a selective adsorption experiment. The adsorption separation method provided by the invention is less influenced by the pH value in the acidic aqueous solution, and has good adsorption effect in the acidic solution with the pH value more than or equal to 2.
Description
Technical Field
The invention belongs to the technical field of adsorption separation of heavy metals, and relates to an adsorbent for adsorbing metal chromium, a preparation method and an adsorption method.
Background
Heavy metal ions such as copper (Cu), cadmium (Cd), lead (Pb), chromium (Cr) and the like cause serious pollution to an ecological system. Although minerals, sediments and the like containing heavy metals in the nature can migrate and transform to the water body along with environmental changes, the heavy metals in industrial wastewater are still main pollution sources of the water body at present. With the development of metallurgical processing, chemical raw materials and product industries, leather and other products, shoemaking industries, metal and electronic product industries, textile industry and other industries, a large amount of industrial wastewater containing heavy metal ions is discharged into natural water bodies, and water resources which are needed by human beings to survive are seriously threatened. In recent years, the total amount of heavy metal emission in industrial wastewater in China is still high, and the heavy metal emission is a potential pollution source, forms a potential threat to human health, and is not slow to treat the heavy metal pollution in water. Chromium is a well-known carcinogen among many heavy metals, wherein the toxicity of Cr (VI) is 100 times that of Cr (III), and Cr (VI) is not naturally degraded in the environment but is easily absorbed by human body, and can invade the human body through digestion, respiratory tract, skin and mucous membrane. Can cause vomiting and abdominal pain when invaded through the digestive tract. Dermatitis and eczema can occur when the skin is immersed. The greatest hazard is the risk of carcinogenesis upon long or short-term contact or inhalation.
Current common chromium-containing wastewater treatment techniques include physicochemical and biological methods such as chemical precipitation, membrane separation, and coagulation flocculation, but they have their inherent advantages and limitations in application. Compared with other treatment technologies, the adsorption method has the advantages of simple operation, good treatment effect, wide application range and the like, and is one of the most extensive methods for removing heavy metals in water at present. In order to ensure sustainable development of water resources and human health, development of efficient, environment-friendly and wide-application-range treatment technologies is an important research direction in the current chromium-containing wastewater treatment field.
However, the traditional adsorbent for treating the chromium-containing wastewater has the defects of complex preparation process, high preparation cost, low adsorption capacity of the adsorbent, high circulation cost and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an adsorbent for adsorbing chromium, a preparation method and an adsorption method. The adsorbent disclosed by the invention has the advantages of good environmental adaptability, high efficiency in preparation process, high adsorption quantity and environment friendliness. According to the invention, tetraethyl silicate and 3-aminopropyl trimethoxy silane are used as main raw materials, reaction conditions are controlled, and amino functional mesoporous silica nano particles with high specific surface area, proper pore diameter and proper particle size are synthesized and used as an adsorbent for adsorbing chromium.
The technical scheme of the invention is as follows:
an adsorbent for adsorbing Cr (VI), wherein the adsorbent is amino-functionalized mesoporous silica nanomaterial.
According to the invention, preferably, the amino-functionalized mesoporous silica nanomaterial is prepared by synthesizing amino-containing mesoporous silica nanomaterial by using tetraethyl silicate and 3-aminopropyl trimethoxy silane as main raw materials, wherein protonated amino in the solution is combined with Cr electrostatic attraction in the solution, so that chromium is removed.
According to the invention, preferably, the amino-functionalized mesoporous silica nanomaterial has a narrow pore size distribution range, and the diameters of the pores are concentrated at 4.2nm.
According to the invention, preferably, the adsorbent has a removal rate of heavy metal Cr (VI) of more than 98% under the conditions that the pH=2, the ratio of the mass of the adsorbent to the volume of the solution is 1mg/mL, the adsorption temperature is 25 ℃ and the contact is sufficient;
preferably, the adsorption of other metals is less than or equal to 10 percent.
According to the present invention, the preparation method of the adsorbent for adsorbing Cr (VI) comprises the following steps:
tetraethyl silicate and 3-aminopropyl trimethoxy silane are used as reaction raw materials, cetyl trimethyl ammonium bromide is used as a template agent, and strong ammonia water is used as a catalyst; after the reaction is finished, removing the template agent, separating the solid, washing the solid, and drying to obtain the amino-functionalized mesoporous silica nanomaterial, namely the adsorbent for adsorbing Cr (VI).
According to the invention, it is preferred that the volume ratio of tetraethyl silicate to 3-aminopropyl trimethoxysilane (1 to 6) is 1, most preferably 4 to 1.
According to the invention, the reaction temperature is preferably from 30℃to 70℃and may be from 30℃to 50℃and 70℃and more preferably 50 ℃.
According to the invention, the reaction time is preferably from 6 to 30 hours; during the reaction, stirring is carried out, preferably at a mechanical stirring rate of 300rpm to 1000rpm.
According to the present invention, the mass concentration of ammonia is preferably 26% to 28%.
According to the invention, the reagent used for removing the template is ethanol and hydrochloric acid in a volume ratio of 11: 1;
preferably, the reagents used for washing the solids are deionized water and absolute ethanol.
According to the invention, the use of the adsorbent for adsorbing Cr (VI) as described above for adsorbing heavy metals Cr (VI).
According to the present invention, the method for adsorbing Cr (vi) using the above adsorbent comprises the steps of:
(1) Adjusting the pH value of the Cr (VI) -containing solution;
(2) Dispersing the adsorbent in the solution obtained in the step (1), and fully mixing and contacting;
(3) Centrifuging the well mixed solution obtained in the step (2), wherein the heavy metal Cr (VI) in the aqueous solution is adsorbed on the adsorption material.
According to the present invention, it is preferable that the pH is adjusted to 1 to 13, preferably to 1 to 12, more preferably to 2 to 6 in the step (1);
preferably, the reagent used for adjusting the pH is hydrochloric acid or sodium hydroxide.
According to the present invention, it is preferable that the adsorption temperature in the step (2) is 25 to 60℃and the adsorption time is 60 to 150 minutes.
Preferably, the mass to volume ratio of the adsorbent to the solution is 0.2 to 1.4 (g/L).
Compared with the prior art, the invention has the advantages and positive effects that:
1. the amino functionalized mesoporous silica nano material is prepared from tetraethyl silicate and 3-aminopropyl trimethoxy silane serving as main raw materials, amino on the material in solution is protonated and then positively charged, and the amino can be combined with negatively charged Cr-containing anions through electrostatic attraction, and simultaneously the protonated amino can be mutually repelled with other positively charged metal ions under an acidic condition, so that the amino functionalized mesoporous silica nano material has good adsorption performance and selectivity.
2. The adsorbent disclosed by the invention is simple in synthesis steps, environment-friendly and good in environmental adaptability and stability.
3. The adsorbent has good adsorption performance and adsorption selectivity to heavy metal Cr (VI), the removal rate of the heavy metal Cr (VI) reaches 98%, and the removal rate of the heavy metal Cr (VI) to other metals is not more than 10%.
4. The Zeta potential of the material surface of the adsorbent has small change along with the pH under the acidic condition; the time for reaching the adsorption equilibrium is very short under the condition of applying external driving force.
Drawings
FIG. 1 is an infrared spectrum characterization of the adsorbent of example 1.
FIG. 2 shows the pore size distribution of the adsorbent in example 1.
FIG. 3 shows the removal rate of 9 different coexisting metal ions by the adsorbent in example 7.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will be more clearly understood, a further description of the invention will be rendered by reference to specific embodiments thereof. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the present invention is not limited to the specific embodiments of the disclosure that follow.
The experimental methods described in the examples below, unless otherwise specified, are all conventional.
The heavy metal mother liquor used in the following examples is a hydrochloric acid solution containing Cr (VI) and/or other metal ions.
After the adsorption separation process is completed, the metal concentration in the solution after centrifugal separation is measured by ICP-OES (inductively coupled plasma emission spectrometer), and the calculation formula of the metal ion removal rate is as follows:
wherein C is 0 And C e (mg/L) represents the concentration of the metal ions in the solution before and after adsorption, respectively.
The adsorption capacity used was calculated as follows:
wherein C is 0 And C e (mg/L) represents the concentration of metal ions in the solution before and after adsorption, respectively; v is the volume of the solution (mL), m is the mass of adsorbent added (mg).
The reagents and materials used in the examples below, unless otherwise specified, were all commercially available.
Example 1
1. Synthesis of amino-functionalized mesoporous silica nanomaterial
Into a 250mL round bottom flask was charged 2.0g of cetyltrimethylammonium bromide, 90mL of deionized water and 20mL of ethylene glycol and the whole system was magnetically stirred at 600rpm for 90min. After the whole system is uniformly stirred, 3mL of ammonia water with the mass concentration of 28% is added, after the ammonia water is added, tetraethyl silicate and 3-aminopropyl trimethoxysilane are added into the reaction system according to a certain volume ratio of X to 1 (X is 1-6), and the total volume of the tetraethyl silicate and the 3-aminopropyl trimethoxysilane is kept to be 3 mL. After the whole system is fed, the initial growth of the nano particles is completed by mechanically stirring for 6 hours under the water bath heating at 50 ℃ and the rotating speed of 600rpm, and at the moment, the solution is observed to have fluorescent blue color under strong lamplight. And then heating in a water bath at 50 ℃ continuously, adjusting the mechanical stirring rotation speed to 300rpm, and stirring in the water bath for 24 hours. And after the reaction is finished, the prepared silicon dioxide nano particles are centrifugally recovered at the rotating speed of 11000rpm, the recovered nano ions are redispersed in a mixed solution of ethanol and hydrochloric acid (the volume ratio of the ethanol to the hydrochloric acid is 11:1), the mixture is centrifugally separated after vortex oscillation is carried out for 1min in a centrifugal tube, and the collected nano particles are dried in a baking oven at 50 ℃ for 12 hours after the vortex oscillation-centrifugal recovery process is repeated for three times. Dispersing the dried nano particles in deionized water, carrying out vortex oscillation cleaning for 1min, carrying out centrifugal separation, carrying out vortex oscillation cleaning for 1min by using absolute ethyl alcohol, carrying out centrifugal separation, carrying out cleaning once by using the deionized water and the absolute ethyl alcohol again, and drying in a drying oven at 50 ℃ for 12 hours to obtain the amino-functionalized mesoporous silica nano material.
Characterizing the synthesized material, and proving that the amino-functionalized silicon dioxide material is successfully synthesized through characteristic peaks in an infrared spectrogram of the attached figure 1; the pore size distribution of the adsorption material is concentrated near 4.2nm in the pore size distribution chart of figure 2, which shows that the adsorption material is mesoporous silica material.
Adsorption process of Cr (VI)
Preparing a Cr (VI) -containing solution: a standard solution of potassium dichromate of 0.0999mol/L was used, diluted to 400mg/L of Cr (VI) -containing solution with deionized water, and added with hydrochloric acid to adjust pH to 2.
10mL of 400mg/L Cr (VI) solution is taken in a centrifuge tube, 10mg of the prepared six adsorbents with different adding proportions (X is 1-6) are added, the adsorbent is adsorbed for 2 hours at 25 ℃ under the mechanical oscillation of 220rpm, the sufficient contact between the adsorbent and the water phase is ensured, centrifugal separation is carried out after the adsorption is finished, the residual concentration of Cr (VI) in the water phase is tested, and the adsorption capacity is calculated.
In the adsorption separation process, when X is 4, the adsorption capacity under the adsorption condition reaches 389.8mg/g; and combining other material characterization and cost consideration, the prepared adsorbent has the best effect when X is 4.
Example 2
1. Synthesis of amino-functionalized mesoporous silica nanomaterial
Into a 250mL round bottom flask was charged 2.0g of cetyltrimethylammonium bromide, 90mL of deionized water and 20mL of ethylene glycol and the whole system was magnetically stirred at 600rpm for 90min. After the whole system is uniformly stirred, 3mL of ammonia water with the mass concentration of 28% is added, after the ammonia water is added, tetraethyl silicate and 3-aminopropyl trimethoxy silane are added into the reaction system according to a certain volume ratio (4:1), and the total volume of the tetraethyl silicate and the 3-aminopropyl trimethoxy silane is kept to be 3 mL. After the whole system is fed, the initial growth of the nano particles is completed by mechanically stirring for 6 hours under the water bath heating at 50 ℃ and the rotating speed of 600rpm, and at the moment, the solution is observed to have fluorescent blue color under strong lamplight. And then heating in a water bath at 50 ℃ continuously, adjusting the mechanical stirring rotation speed to 300rpm, and stirring in the water bath for 24 hours. And after the reaction is finished, the prepared silicon dioxide nano particles are centrifugally recovered at the rotating speed of 11000rpm, the recovered nano ions are redispersed in a mixed solution of ethanol and hydrochloric acid (the volume ratio of the ethanol to the hydrochloric acid is 11:1), the mixture is centrifugally separated after vortex oscillation is carried out for 1min in a centrifugal tube, and the collected nano particles are dried in a baking oven at 50 ℃ for 12 hours after the vortex oscillation-centrifugal recovery process is repeated for three times. Dispersing the dried nano particles in deionized water, carrying out vortex oscillation cleaning for 1min, carrying out centrifugal separation, carrying out vortex oscillation cleaning for 1min by using absolute ethyl alcohol, carrying out centrifugal separation, carrying out cleaning once by using the deionized water and the absolute ethyl alcohol again, and drying in a drying oven at 50 ℃ for 12 hours to obtain the amino-functionalized mesoporous silica nano material.
Adsorption process of Cr (VI)
Preparing a Cr (VI) -containing solution: a standard solution of potassium dichromate of 0.0999mol/L was used. The solution containing Cr (VI) is diluted with deionized water to 100mg/L, 200mg/L, 400mg/L, 600mg/L, 800mg/L, 1400mg/L, 1600mg/L, 2000mg/L, 2400mg/L, 2800mg/L, 3200mg/L and 3600mg/L respectively, and hydrochloric acid is added to adjust the pH to 2.
10mL of Cr (VI) solution with different concentrations is respectively taken in a centrifuge tube, 10mg of the prepared adsorbent is added, the adsorbent is adsorbed for 2 hours at 25 ℃ under mechanical oscillation of 220rpm, the sufficient contact between the adsorbent and the water phase is ensured, centrifugal separation is carried out after the adsorption is finished, the residual concentration of Cr (VI) in the water phase is tested, and the adsorption capacity is calculated. And obtaining the corresponding relation between the equilibrium concentration and the adsorption capacity.
In the adsorption separation process, the adsorption capacity obtained after adsorption under Cr (VI) solutions with different concentrations is plotted with the equilibrium concentration, and the maximum adsorption capacity is 2410.9mg/g through Langmuir adsorption isotherm fitting.
Example 3
1. Synthesis of amino-functionalized mesoporous silica nanomaterial
The method for synthesizing nanomaterial in this embodiment is specifically described in embodiment 2.
Adsorption process of Cr (VI)
Preparing a Cr (VI) -containing solution: the standard solution of potassium dichromate of 0.0999mol/L is used, deionized water is used for diluting the solution to 400mg/L of Cr (VI) containing solution, and hydrochloric acid or sodium hydroxide solution is added for regulating the pH value to be 1-12 respectively.
The main existence form of Cr (VI) in aqueous solutions with different pH values is as follows: cr (VI) is treated with HCrO at pH 7 or less 4 - 、Cr 2 O 7 2- Exists as HCrO 4 - Mainly comprises; cr (VI) is CrO when the pH is more than or equal to 7 4 2- 、HCrO 4 - Exists as CrO 4 2- Mainly. Respectively taking 10mL of Cr (VI) solutions with different pH values into a centrifuge tube,10mg of the prepared adsorbent is added, the adsorbent is adsorbed for two hours at 25 ℃ and 220rpm under mechanical oscillation to ensure that the adsorbent is fully contacted with the water phase, centrifugal separation is carried out after the adsorption is finished, the residual concentration of Cr (VI) in the water phase is tested, and the adsorption capacity and the removal rate at different initial pH values are calculated.
TABLE 1 adsorption Capacity of adsorbents for Cr (VI) at pH different
In the adsorption separation process, the adsorption capacity of Cr (VI) is shown in Table 1 under different pH conditions, and the adsorption capacity of the adsorbent for Cr (VI) is increased and then decreased with the increase of the pH, and the adsorption capacity of the adsorbent for Cr (VI) is kept at a higher level in an acidic range with the pH being more than 2.
Example 4
1. Synthesis of amino-functionalized mesoporous silica nanomaterial
The method for synthesizing nanomaterial in this embodiment is specifically described in example 2
Adsorption process of Cr (VI)
Preparing a Cr (VI) -containing solution: a standard solution of potassium dichromate of 0.0999mol/L was used, diluted to 400mg/L of Cr (VI) containing solution with deionized water, and the pH was adjusted to 2 with the addition of hydrochloric acid.
Respectively taking 10mL of the Cr (VI) solution into a centrifuge tube, adding 10mg of the prepared adsorbent, and heating at different temperatures of 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃,50 ℃, 55 ℃ and 60 ℃; the adsorption was carried out for two hours under mechanical shaking at 220rpm to ensure sufficient contact of the adsorbent with the aqueous phase, the centrifugal separation was carried out after completion of the adsorption, the residual concentration of Cr (VI) in the aqueous phase was tested, and the adsorption capacity and removal rate at different temperatures were calculated.
In the adsorption separation process, the adsorption capacity of Cr (VI) is shown in Table 2 under different temperature conditions, and the adsorption capacity of the adsorbent for Cr (VI) gradually decreases with the increase of temperature, but is at a higher level.
TABLE 2 adsorption Capacity of adsorbents for Cr (VI) at different temperatures
| Temperature (. Degree. C.) | 25 | 30 | 35 | 40 | 45 | 50 | 55 | 60 |
| Adsorption capacity (mg/g) | 389 | 379 | 376 | 374 | 371 | 368 | 366 | 365 |
Example 5
1. Synthesis of amino-functionalized mesoporous silica nanomaterial
The method for synthesizing nanomaterial in this embodiment is specifically described in example 2
Adsorption process of Cr (VI)
Preparing a Cr (VI) -containing solution: a standard solution of potassium dichromate of 0.0999mol/L was used, diluted to 600mg/L of Cr (VI) containing solution with deionized water, and the pH was adjusted to 2 with the addition of hydrochloric acid.
10mL of the Cr (VI) solution is respectively taken in a centrifuge tube, 2mg, 4mg, 6mg, 8mg, 10mg, 12mg and 14mg of the prepared adsorbent are respectively added into the centrifuge tube, the adsorbent is fully contacted with water phase after being adsorbed for two hours under the mechanical oscillation of 220rpm at 25 ℃, centrifugal separation is carried out after the adsorption is finished, the residual concentration of Cr (VI) in the water phase is tested, and the adsorption capacity and the removal rate under different adsorbent amounts are calculated.
In the adsorption separation process, the removal rate of Cr (VI) by the adsorbent increases with the increase of the dosage under the condition that different amounts of the adsorbent are added. The results are shown in Table 3.
TABLE 3 removal of Cr (VI) by adsorbents of different masses
| Adsorbent amount (mg) | 2 | 4 | 6 | 8 | 10 | 12 | 14 |
| Removal rate of | 79.5％ | 92.9％ | 95.9％ | 97.3％ | 97.8％ | 98.3％ | 98.6％ |
Example 6
1. Synthesis of amino-functionalized mesoporous silica nanomaterial
The method for synthesizing nanomaterial in this embodiment is specifically described in example 2
Adsorption process of Cr (VI)
Preparing a Cr (VI) -containing solution: the Cr (VI) containing solution was diluted with deionized water to 200mg/L using 0.0999mol/L potassium dichromate standard solution to prepare Cl containing Cr (VI) at 200mg/L and 4 different concentrations (0 mM, 5mM, 10mM, 20 mM), respectively - ，SO 4 2- ，NO 3 - The pH of the solution was adjusted to 2.
10mL of the Cr (VI) solution is respectively taken in a centrifuge tube, 10mg of the prepared adsorbent is added, the adsorbent is adsorbed for two hours under the mechanical oscillation of 220rpm at 25 ℃ to ensure that the adsorbent is fully contacted with water phase, centrifugal separation is carried out after the adsorption is finished, and the residual concentration of Cr (VI) in the water phase is tested.
In the adsorption separation process, cl with different concentrations - ，SO 4 2- ，NO 3 - Has certain influence on the adsorption capacity of the adsorbent, wherein SO 4 2- Maximum effect, NO 3 - Influencing next, cl - The influence of (2) is minimal. The results are shown in Table 4.
TABLE 4 influence of Co-existing anions at different concentrations on the adsorption capacity of adsorbents
| Concentration/adsorption capacity | Cl - | SO 4 2- | NO 3 - |
| 0mM | 195mg/g | 195mg/g | 195mg/g |
| 5mM | 194mg/g | 118mg/g | 193mg/g |
| 10mM | 193mg/g | 100mg/g | 191mg/g |
| 20mM | 191mg/g | 97mg/g | 181mg/g |
Example 7
1. Synthesis of amino-functionalized mesoporous silica nanomaterial
The method for synthesizing nanomaterial in this embodiment is specifically described in example 2
Adsorption process of Cr (VI)
Preparing a multi-metal solution: a multi-metal mixed solution containing Fe (III), ni (II), mn (II), cu (II), zn (II), mg (II), co (II), cr (VI) and Cd (II) with the concentration of 100Mg/L is prepared by using a standard solution of potassium dichromate with the concentration of 0.0999mol/L, and hydrochloric acid is added to adjust the pH value to 2.
10mL of the multi-metal solution is respectively taken in a centrifuge tube, 10Mg of the prepared adsorbent is added, the adsorbent is adsorbed for two hours under the mechanical oscillation of 220rpm at 25 ℃ to ensure that the adsorbent is fully contacted with the water phase, centrifugal separation is carried out after the adsorption is finished, and the residual concentration of Fe (III), ni (II), mn (II), cu (II), zn (II), mg (II), co (II), cr (VI) and Cd (II) in the water phase is tested.
In the adsorption separation process, the removal rate of each metal is shown in fig. 3, and it can be seen from fig. 3: the removal rate of the adsorbent to Cr (VI) is up to 98%, the removal rates of Ni (II), mn (II), cu (II), zn (II), co (II) and Cd (II) are not more than 5%, and the removal rates of Fe (III) and Mg (II) are not more than 10%. Therefore, the adsorbent has good selectivity for adsorbing and removing Cr (VI).
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention without departing from the technical content of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (6)
1. The preparation method of an adsorbent for adsorbing Cr (VI), wherein the adsorbent is prepared by synthesizing amino-containing mesoporous silica nano material by taking tetraethyl silicate and 3-aminopropyl trimethoxy silane as main raw materials;
the method comprises the following steps:
tetraethyl silicate and 3-aminopropyl trimethoxy silane are used as reaction raw materials, cetyl trimethyl ammonium bromide is used as a template agent, and strong ammonia water is used as a catalyst; after the reaction is finished, removing a template agent, separating solids, washing the solids, and drying to obtain an amino-functionalized mesoporous silica nanomaterial, namely an adsorbent for adsorbing Cr (VI);
the reaction temperature is 30-70 ℃, the reaction time is 6-30 hours, the mass concentration of ammonia water is 26-28%, and the reagent for removing the template agent is ethanol and hydrochloric acid according to the volume ratio of 11:1, and the reagents used for washing the solid are deionized water and absolute ethyl alcohol.
2. The method for preparing the adsorbent for adsorbing Cr (VI) according to claim 1, wherein the pore size of the amino-functionalized mesoporous silica nanomaterial is concentrated and distributed in 4.2. 4.2nm.
3. The method for preparing the adsorbent for adsorbing Cr (VI) according to claim 1, wherein the adsorbent has a mass-to-volume ratio of 1mg/mL at a pH=2, an adsorption temperature of 25 ℃, and a removal rate of 98% or more for heavy metal Cr (VI) and less than or equal to 10% for other metals under the condition of sufficient contact.
4. The method for producing an adsorbent for adsorbing Cr (VI) according to claim 1, wherein the ratio by volume of tetraethyl silicate to 3-aminopropyl trimethoxysilane is 1 to 6.
5. A method for adsorbing Cr (vi) comprising using the adsorbent prepared according to claim 1, comprising the steps of:
(1) Adjusting the pH value of the Cr (VI) -containing solution;
(2) Dispersing the adsorbent in the solution obtained in the step (1), and fully mixing and contacting;
(3) Centrifuging the well mixed solution obtained in the step (2), wherein the heavy metal Cr (VI) in the aqueous solution is adsorbed on the adsorption material.
6. The method for adsorbing Cr (VI) according to claim 5, wherein the pH is adjusted to 1 to 13 in the step (1); the adsorption temperature in the step (2) is 25-60 ℃ and the adsorption time is 60-150min.
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| CN101088597A (en) * | 2006-06-13 | 2007-12-19 | 中国科学院过程工程研究所 | Adsorbent for adsorbing six-valent chromium ion and its prepn process |
| CN106076279A (en) * | 2016-08-26 | 2016-11-09 | 汪竹青 | A kind of adsorbent for heavy metal and its preparation method and application |
| CN110064358A (en) * | 2019-05-08 | 2019-07-30 | 广州大学 | SiO of the one kind for toxicity Cr (VI) absorption2/ γ-AlOOH laminated film and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088597A (en) * | 2006-06-13 | 2007-12-19 | 中国科学院过程工程研究所 | Adsorbent for adsorbing six-valent chromium ion and its prepn process |
| CN106076279A (en) * | 2016-08-26 | 2016-11-09 | 汪竹青 | A kind of adsorbent for heavy metal and its preparation method and application |
| CN110064358A (en) * | 2019-05-08 | 2019-07-30 | 广州大学 | SiO of the one kind for toxicity Cr (VI) absorption2/ γ-AlOOH laminated film and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| NH_2-MCM-41吸附剂的制备及其对铬离子(Ⅵ)吸附行为的研究;郭宇;苗世举;吴红梅;肖昱;;现代化工(06);95-100 * |
| 氨基功能化多孔材料吸附二氧化碳研究进展;李晓玉等;《材料导报》;32;208-213、219 * |
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