CN112958043A - Preparation method of goethite/carboxylated cellulose nanocrystalline composite material for removing heavy metal ions - Google Patents

Preparation method of goethite/carboxylated cellulose nanocrystalline composite material for removing heavy metal ions Download PDF

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CN112958043A
CN112958043A CN202110147157.7A CN202110147157A CN112958043A CN 112958043 A CN112958043 A CN 112958043A CN 202110147157 A CN202110147157 A CN 202110147157A CN 112958043 A CN112958043 A CN 112958043A
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goethite
composite material
heavy metal
carboxylated cellulose
metal ions
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CN112958043B (en
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滕玮
陈燕燕
付融冰
范建伟
张伟贤
陈小倩
马倩
薛英浩
冉献强
孙宇
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Tongji University
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract

The invention provides a preparation method of a goethite/carboxylated cellulose nanocrystal composite material for removing heavy metal ions, wherein the heavy metal ions are in heavy metal wastewater, the composite material provided by the invention is formed by compounding goethite and carboxylated cellulose nanocrystals by a hydrothermal method, the problems that the goethite is easy to agglomerate, the cellulose nanocrystals are difficult to separate and the like are solved, and the adsorption capacity on the heavy metal ions is improved. The composite material obtained by the preparation method has higher adsorption capacity and higher adsorption rate on heavy metal ions such As Pb (II), Cd (II), As (V) and the like. The method has the advantages of cheap and easily-obtained raw materials, simple preparation process and mild conditions, and the prepared goethite/carboxylated cellulose nanocrystalline composite material is a heavy metal adsorbent with excellent performance and low cost and has good application prospect.

Description

Preparation method of goethite/carboxylated cellulose nanocrystalline composite material for removing heavy metal ions
Technical Field
The invention belongs to the technical field of new environmental functional materials and heavy metal wastewater treatment, and particularly relates to a preparation method of a goethite/carboxylated cellulose nanocrystalline composite material for removing heavy metal ions.
Background
In recent years, the discharge of wastewater generated by industries such as mineral resource development, electroplating, metal processing and smelting, tanning, fertilizer production and the like and the application of fertilizers and pesticides in agricultural activities cause a large amount of heavy metals to be released into the environment, so that the heavy metal pollution of water bodies is aggravated. Heavy metals are highly toxic and non-biodegradable, and once entering water, they cause long-term pollution of water ecosystem, and can enter human body and other living organisms through drinking water and food chain to accumulate, causing irreversible harm to human health and ecological environment, for example, cadmium (Cd) has been proved to be related to pathogenesis of osteodynia, myocardial infarction, hypertension, etc., arsenic (As) causes skin cancer, cardiovascular and respiratory system diseases, etc., and lead (Pb) is related to initiation of anorexia, learning disorder, etc. The removal of toxic heavy metal ions from water and wastewater is therefore an important task for protecting public health and the environment.
The adsorption method is simple and convenient to operate, and is an economic, efficient and mature heavy metal wastewater treatment method. Iron-based materials, e.g. Fe0，FeOOH，Fe2O3FeS and the like have been widely used for heavy metal wastewater treatment. The iron oxide has large surface area, strong reactivity and strong removal capacity to heavy metal, particularly goethite (alpha-FeOOH) is a ubiquitous natural mineral in soil/sediments, is relatively stable, has low cost, high specific surface area and a large amount of hydroxyl groups, and has strong adsorption capacity to heavy metal ions. However, the single goethite particles are fine and are easy to agglomerate in an aqueous solution, so that the surface activity of the single goethite particles is reduced, the adsorption performance is weakened, and the application of the single goethite particles is limited to a certain extent.
The cellulose is the most abundant natural polymer material in nature, has the advantages of biodegradability, no toxicity, easy modification, renewability and the like, and has better application prospect in the fields of biomedicine, energy, environment and the like. The nano-cellulose is extracted from a cellulose raw material by methods such as chemical hydrolysis, mechanical crushing, enzymolysis and the like, wherein the cellulose nano-crystal has higher crystallinity and stronger rigidity, chemical stability and thermal stability. However, the cellulose nanocrystals in the prior art have small size and high dispersibility in water, and are difficult to separate after the reaction for removing heavy metals in sewage is completed.
Disclosure of Invention
Aiming at the defects, the invention provides a goethite/carboxylated cellulose nanocrystal composite material synthesized by a hydrothermal method, solves the problems of agglomeration of goethite and difficult separation of cellulose nanocrystals, and is applied to adsorption of heavy metal ions in wastewater. The composite material prepared by the invention has higher adsorption capacity and higher adsorption rate to heavy metal ions.
The invention provides the following technical scheme: the preparation method of the goethite/carboxylated cellulose nanocrystalline composite material for removing the heavy metal ions comprises the following steps:
(1) dispersing 32.5g of 3.2 wt% carboxylated cellulose nanocrystals into 67.5g of deionized water at room temperature, and magnetically stirring for 20min to form 1 wt% carboxylated cellulose nanocrystal dispersion;
(2) adding Fe (NO) to the dispersion obtained in the step (1)3)3·9H2O, chamberMagnetically stirring for 8h at room temperature to obtain Fe3+A carboxylated cellulose nanocrystal complexing mixed solution;
(3) adding a NaOH solution with the concentration of 5M into the mixed solution obtained in the step (2) while stirring to adjust the pH of the mixed solution, and continuously stirring for 30 s;
(4) and (4) transferring the mixed solution obtained in the step (3) to a hydrothermal reaction kettle, sealing, placing the hydrothermal reaction kettle in an oven for hydrothermal reaction, washing the obtained product after the reaction is finished, and placing the product in a vacuum drying oven for drying at 50 ℃ for 12 hours to finally obtain the goethite/carboxylated cellulose nanocrystalline composite material.
Further, Fe (NO) added in the step (2)3)3·9H2The mass of O is 0-10 g.
Further, in the step (3), the pH of the mixed solution is adjusted to be more than 13.
Further, the hydrothermal reaction condition in the step (4) is 70 ℃ for 12 hours.
Further, after the reaction in the step (4) is finished, washing the obtained product is to repeatedly wash the obtained product with deionized water to be neutral, and then washing with absolute ethyl alcohol for 2-3 times.
Further, the goethite/carboxylated cellulose nanocrystalline composite material can remove one or more heavy metal ions of Pb (II), Cd (II) or As (V) in heavy metal wastewater.
The invention has the beneficial effects that:
1. the goethite has high specific surface area and a complex surface structure, particularly contains a large number of hydroxyl functional groups on the surface, and has strong adsorption capacity on various negative and positive ions and organic pollutants in water, particularly heavy metal ions. The synthesized goethite has fine particles, and the cellulose nanocrystalline with high dispersibility is used as a carrier, so that the goethite can be effectively dispersed, the phenomenon that the goethite is easy to agglomerate when being independently applied to wastewater treatment to reduce the surface activity and further weaken the adsorption performance of the goethite is overcome, and the removal capacity of the goethite to pollutants is enhanced.
2. Compared with other existing carrier materials, the carboxylated cellulose nanocrystal contains a large number of surfacesThe functional group and the dispersity are high, the rigidity, the chemical stability and the thermal stability are high, and the carrier serving as goethite mainly has the following advantages: (1) having a large number of carboxyl functions on the surface, Fe3+Can carry out electrostatic interaction with carboxyl functional groups to load Fe element on carboxylated cellulose nanocrystalline, and is beneficial to Fe3+Binding to a carrier; (2) the high dispersibility in water is beneficial to the fixation and dispersion of goethite; (3) the catalyst has stronger rigidity and stability, can reduce the dissolution of goethite, and prolongs the service life of the adsorbent; (4) has biodegradability, no toxicity, low price and easy obtainment.
3. Carboxyl functional groups on the surface of the carboxylated cellulose nanocrystal have a certain adsorption effect on heavy metal ions, and after the carboxyl functional groups are combined with goethite, the effect of removing the heavy metal ions can be improved, and the defects that the dispersion of the carboxyl functional groups in water is high and solid-liquid separation is difficult to perform after adsorption are overcome.
4. The goethite/carboxylated cellulose nanocrystalline composite material prepared by the invention has higher adsorption capacity and faster reaction rate on heavy metal cations and heavy metal oxygen-containing acid radicals in the process of removing wastewater containing heavy metal ions.
5. The preparation method is simple and easy to operate, mild in preparation conditions, low in cost and wide in application prospect.
Drawings
The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings. Wherein:
fig. 1 is an X-ray diffraction (XRD) spectrum of a carboxylated cellulose nanocrystalline material provided in example 1 of the present invention;
fig. 2 is an X-ray diffraction (XRD) spectrum of the goethite/carboxylated cellulose nanocrystal composite provided in example 1 of the present invention;
figure 3 is an X-ray diffraction (XRD) spectrum of the goethite material provided in example 1 of the present invention;
FIG. 4 is a graph showing the adsorption amount of Pb (II) at room temperature for various goethite/carboxylated cellulose nanocrystal composites provided in example 1 of the present invention;
FIG. 5 shows the adsorption of Cd (II) at room temperature for different goethite/carboxylated cellulose nanocrystal composites provided in example 1 of the present invention;
FIG. 6 is a graph showing the adsorption amount of As (V) at room temperature for various goethite/carboxylated cellulose nanocrystal composites provided in example 1 of the present invention;
FIG. 7 is a graph showing the adsorption kinetics of goethite/carboxylated cellulose nanocrystal composite material for Pb (II) at room temperature, as provided in example 2 of the present invention;
FIG. 8 is a graph showing the adsorption effect of goethite/carboxylated cellulose nanocrystal composite material on wastewater containing Pb (II) at different concentrations at room temperature, which is provided in example 2 of the present invention;
FIG. 9 is a graph showing the adsorption kinetics of Cd (II) at room temperature for goethite/carboxylated cellulose nanocrystal composites provided in example 3 of the present invention;
FIG. 10 shows the adsorption effect of goethite/carboxylated cellulose nanocrystal composite material on wastewater containing Cd (II) with different concentrations at room temperature, which is provided in example 3 of the present invention;
FIG. 11 is a graph showing the adsorption kinetics of goethite/carboxylated cellulose nanocrystal composite material for As (V) at room temperature, As provided in example 4 of the present invention;
fig. 12 shows the adsorption effect of goethite/carboxylated cellulose nanocrystal composite material on As (v) -containing wastewater with different concentrations at room temperature, which is provided in example 4 of the present invention.
Detailed description of the preferred embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 embodiment provides a goethite/carboxylated cellulose nanocrystalline composite material and a preparation method thereof, and the preparation method comprises the following steps:
(1) 32.5g of 3.2 wt% carboxylated cellulose nanocrystals were dispersed in 67.5g of deionized water at room temperature, and magnetically stirred for 20min to form a 1 wt% carboxylated cellulose nanocrystal dispersion.
(2) Adding 1-10 g of Fe (NO) into the dispersion liquid obtained in the step (1)3)3·9H2O, magnetically stirring for 8 hours at room temperature to obtain Fe3+The carboxylated cellulose nanocrystalline complex mixed solution.
(3) Adding a 5M NaOH solution into the mixed solution obtained in the step (2) while stirring to adjust the pH of the mixed solution to be more than 13, and continuing stirring for 30 s.
(4) And (3) transferring the mixed solution obtained in the step (3) into a hydrothermal reaction kettle, sealing, placing the hydrothermal reaction kettle in an oven for hydrothermal reaction for 12 hours at 70 ℃, repeatedly washing the product to be neutral by using deionized water after the reaction is finished, washing the product for 2-3 times by using absolute ethyl alcohol, and placing the product in a vacuum drying oven for drying for 12 hours at 50 ℃ to finally obtain the goethite/carboxylated cellulose nanocrystalline composite material. Different Fe (NO)3)3·9H2The goethite/carboxylated cellulose nanocrystalline composite material with the added O mass is expressed by alpha-FeOOH/C-CNC-x, wherein x represents Fe (NO)3)3·9H2Addition quality of O (i.e., x g of Fe (NO) was added to the dispersion in preparation step (2) of example 1)3)3·9H2O), x is respectively 1, 2, 4 and 10), the original carboxylated cellulose nanocrystal is expressed by C-CNC, and the non-carboxylated cellulose nanocrystal is expressed by alpha-FeOOH for the goethite using as a carrier. The crystal structure of the material is characterized by an X-ray diffraction method (XRD), and the characterization result is shown in figures 1-3.
FIG. 1 is an X-ray diffraction (XRD) spectrum of a primary carboxylated cellulose nanocrystal, with diffraction peaks at 15.0 and 22.8 degrees 2 theta coinciding with the standard spectrum PDF #50-2241 of cellulose. Fig. 2 is an X-ray diffraction (XRD) spectrum of the finally obtained goethite/carboxylated cellulose nanocrystal composite material. As can be seen from the figure, with Fe (NO)3)3·9H2The impregnation of O on the carboxylated cellulose nanocrystals destroyed the crystal structure of the carboxylated cellulose nanocrystals, with a 2 θ angle of 15.0. The diffraction peak near 22.8 degrees disappeared. Fe (NO)3)3·9H2When the adding amount of O is 1-4 g, the content of goethite is relatively low, and the characteristic peak of the goethite is still weak. When Fe (NO)3)3·9H2When the adding amount of O is increased to 10g, the alpha-FeOOH/C-CNC-10 has obvious diffraction peaks at the 2 theta angles of 21.2, 33.2, 34.7, 36.6, 53.2 degrees and the like, and is matched with the characteristic absorption peaks of goethite (PDF #29-0713), and the peaks respectively correspond to the (110), (130), (021), (111) and (221) crystal faces of the goethite, so that the goethite is successfully loaded on the carboxylated cellulose nanocrystal. Fig. 3 is an XRD spectrum of goethite prepared by the same method, which is consistent with the standard spectrum PDF #29-0713 of goethite, and the diffraction peak is strong, confirming that it is goethite.
The goethite/carboxylated cellulose nanocrystalline composite material prepared in example 1 was subjected to heavy metal wastewater treatment, represented by the heavy metal ions of Pb (ii), Cd (ii), and As (v), a certain amount of the composite material was added to heavy metal-containing simulated wastewater of a certain volume and a certain initial concentration, and the Pb (ii) concentration before and after the reaction was measured by an inductively coupled plasma emission spectrometer (ICP-OES). The experimental parameters were as follows:
the dosage of the composite material is 10 mg;
the initial concentrations of the Pb (II), Cd (II) and As (V) simulated wastewater are respectively 50, 20 and 10 mg.L-1Volume is 40mL, pH is-5;
the reaction temperature is 25 ℃ at room temperature, the reaction time is 1h, and the rotating speed of a shaking table is 200rpm min-1；
The adsorption amounts of the composite material prepared in example 1 to different heavy metal ions are shown in fig. 4 to 6. As can be seen from the graphs in FIGS. 4-6, the adsorption capacity of alpha-FeOOH/C-CNC-1 to Pb (II) and Cd (II) is obviously better than that of C-CNC and alpha-FeOOH, and the adsorption capacity to As (V) is obviously higher than that of C-CNC but slightly lower than that of alpha-FeOOH, so that the goethite/carboxylated cellulose nanocrystalline composite material prepared by combining C-CNC and alpha-FeOOH can obviously improve the adsorption performance of the material to heavy metal ions on the whole. With Fe (NO)3)3·9H2Further increase of the addition amount of O, the composite materialSlightly reduces the adsorption amount of three heavy metal ions, and Fe (NO) as a precursor of iron3)3·9H2The alpha-FeOOH/C-CNC-1 with the adding amount of O of 1g is the optimal composite material.
Example 2
(1) 32.5g of 3.2 wt% carboxylated cellulose nanocrystals were dispersed in 67.5g of deionized water at room temperature, and magnetically stirred for 20min to form a 1 wt% carboxylated cellulose nanocrystal dispersion.
(2) Adding 1g of Fe (NO) to the dispersion obtained in the step (1)3)3·9H2O, magnetically stirring for 8 hours at room temperature to obtain Fe3+The carboxylated cellulose nanocrystalline complex mixed solution.
(3) Adding a 5M NaOH solution into the mixed solution obtained in the step (2) while stirring to adjust the pH of the mixed solution to be more than 13, and continuing stirring for 30 s.
(4) And (3) transferring the mixed solution obtained in the step (3) into a hydrothermal reaction kettle, sealing, placing the hydrothermal reaction kettle in an oven for hydrothermal reaction for 12 hours at 70 ℃, repeatedly washing the product to be neutral by using deionized water after the reaction is finished, washing the product for 2-3 times by using absolute ethyl alcohol, and placing the product in a vacuum drying oven for drying for 12 hours at 50 ℃ to finally obtain the goethite/carboxylated cellulose nanocrystalline composite material (alpha-FeOOH/C-CNC-1).
The goethite/carboxylated cellulose nanocrystalline composite material prepared in example 2 was subjected to heavy metal wastewater treatment, represented by Pb (ii) as a heavy metal ion, a certain amount of the composite material was added to Pb (ii) -containing heavy metal simulated wastewater of a certain volume and different initial concentrations, and the Pb (ii) concentrations before and after the reaction were measured by an inductively coupled plasma emission spectrometer (ICP-OES). The experimental parameters were as follows:
the dosage of the composite material is 10 mg;
the initial concentration of the Pb (II) simulated wastewater is 10-100 mg.L-1Volume 40mL, pH-5 (original solution without pH adjustment);
the reaction temperature is 25 ℃ at room temperature, the reaction time is 0-5 h, and the rotating speed of a shaking table is 200rpm min-1；
The composite material prepared in example 2 isThe amounts of adsorbed Pb (II) at different reaction times and the amounts of adsorbed Pb (II) at different initial concentrations are shown in FIGS. 7 and 8, respectively. As can be seen from FIG. 7, the adsorption amount of Pb (II) by α -FeOOH/C-CNC-1 shows a tendency of rapidly increasing and then leveling off as the adsorption time increases. Within 5min before the adsorption, the adsorption amount of Pb (II) rapidly increased, and thereafter the curve gradually became gentle. The increase of the adsorption quantity is less, and the adsorption reaches the balance in about 30 min. As can be seen from FIG. 8, the initial concentration of Pb (II) is 10 to 50 mg.L-1When the initial concentration of Pb (II) is increased, the adsorption amount of Pb (II) by the composite material is increased, and the adsorption amount is basically unchanged along with the increase of the initial concentration of Pb (II). When the initial concentration of Pb (II) is 50 mg.L-1When the composite material is used, the adsorption capacity of the composite material to Pb (II) can reach 133 mg/g-1。
Example 3
(1) 32.5g of 3.2 wt% carboxylated cellulose nanocrystals were dispersed in 67.5g of deionized water at room temperature, and magnetically stirred for 20min to form a 1 wt% carboxylated cellulose nanocrystal dispersion.
(2) Adding 1g of Fe (NO) to the dispersion obtained in the step (1)3)3·9H2O, magnetically stirring for 8 hours at room temperature to obtain Fe3+The carboxylated cellulose nanocrystalline complex mixed solution.
(3) Adding a 5M NaOH solution into the mixed solution obtained in the step (2) while stirring to adjust the pH of the mixed solution to be more than 13, and continuing stirring for 30 s.
(4) And (3) transferring the mixed solution obtained in the step (3) into a hydrothermal reaction kettle, sealing, placing the hydrothermal reaction kettle in an oven for hydrothermal reaction for 12 hours at 70 ℃, repeatedly washing the product to be neutral by using deionized water after the reaction is finished, washing the product for 2-3 times by using absolute ethyl alcohol, and placing the product in a vacuum drying oven for drying for 12 hours at 50 ℃ to finally obtain the goethite/carboxylated cellulose nanocrystalline composite material (alpha-FeOOH/C-CNC-1).
The goethite/carboxylated cellulose nanocrystalline composite material prepared in example 3 was subjected to heavy metal wastewater treatment, Cd (ii) was taken as a heavy metal ion representative, a certain amount of the composite material was added to Cd (ii) -containing heavy metal simulated wastewater of a certain volume and different initial concentrations, and the concentrations of Cd (ii) before and after the reaction were measured by an inductively coupled plasma emission spectrometer (ICP-OES). The experimental parameters were as follows:
the dosage of the composite material is 10 mg;
the initial concentration of the Cd (II) simulated wastewater is 5-50 mg.L-1Volume 40mL, pH-5 (original solution without pH adjustment);
the reaction temperature is 25 ℃ at room temperature, the reaction time is 0-5 h, and the rotating speed of a shaking table is 200rpm min-1；
The adsorption amounts of the composite material prepared in example 3 to Cd (II) at different reaction times and the adsorption amounts to Cd (II) at different initial concentrations are respectively shown in FIGS. 9 and 10. As can be seen from FIG. 9, the adsorption amount of Cd (II) by alpha-FeOOH/C-CNC-1 shows a tendency of rapidly increasing and then becoming stable with the increase of the adsorption time. Within 5min before adsorption, the adsorption quantity of Cd (II) is rapidly increased, and the curve gradually becomes gentle thereafter. The increase of the adsorption quantity is less, and the adsorption reaches the balance in about 30 min. As can be seen from FIG. 10, the initial concentration of Cd (II) is 5-20 mg.L-1Meanwhile, the adsorption capacity of the composite material to Cd (II) is increased along with the increase of the initial concentration of Cd (II), and the change of the adsorption capacity is smaller along with the increase of the initial concentration of Cd (II). When the initial concentration of Cd (II) is 20 mg.L-1When the adsorption capacity of the composite material to Cd (II) can reach 59 mg/g-1。
Example 4
(1) 32.5g of 3.2 wt% carboxylated cellulose nanocrystals were dispersed in 67.5g of deionized water at room temperature, and magnetically stirred for 20min to form a 1 wt% carboxylated cellulose nanocrystal dispersion.
(2) Adding 1g of Fe (NO) to the dispersion obtained in the step (1)3)3·9H2O, magnetically stirring for 8 hours at room temperature to obtain Fe3+The carboxylated cellulose nanocrystalline complex mixed solution.
(3) Adding a 5M NaOH solution into the mixed solution obtained in the step (2) while stirring to adjust the pH of the mixed solution to be more than 13, and continuing stirring for 30 s.
(4) And (3) transferring the mixed solution obtained in the step (3) into a hydrothermal reaction kettle, sealing, placing the hydrothermal reaction kettle in an oven for hydrothermal reaction for 12 hours at 70 ℃, repeatedly washing the product to be neutral by using deionized water after the reaction is finished, washing the product for 2-3 times by using absolute ethyl alcohol, and placing the product in a vacuum drying oven for drying for 12 hours at 50 ℃ to finally obtain the goethite/carboxylated cellulose nanocrystalline composite material (alpha-FeOOH/C-CNC-1).
The goethite/carboxylated cellulose nanocrystalline composite material prepared in example 4 was subjected to heavy metal wastewater treatment, As (v) was used As a heavy metal ion representative, a certain amount of the composite material was added to heavy metal simulated wastewater containing As (v) in a certain volume and at different initial concentrations, and the concentration of As (v) before and after the reaction was measured by using an inductively coupled plasma emission spectrometer (ICP-OES). The experimental parameters were as follows:
the dosage of the composite material is 10 mg;
the initial concentration of the As (V) simulated wastewater is 2-20 mg.L-1Volume is 40mL, pH is-4;
the reaction temperature is 25 ℃ at room temperature, the reaction time is 0-5 h, and the rotating speed of a shaking table is 200rpm min-1；
The adsorption amounts of the composite material prepared in example 4 for As (V) and the adsorption amounts for As (V) at different initial concentrations at different reaction times are shown in FIGS. 11 and 12, respectively. As can be seen from FIG. 11, the adsorption amount of As (V) by α -FeOOH/C-CNC-1 shows a tendency of rapidly increasing and then smoothing with the increase of the adsorption time. The adsorbed amount of As (V) rapidly increased within 30min before adsorption, and the curve gradually became gentle thereafter. The increase of the adsorption quantity is less, and the adsorption reaches the balance in about 60 min. As can be seen from FIG. 12, the initial concentration of As (V) is 2 to 20 mg.L-1In this case, As the initial concentration of As (V) increases, the amount of As (V) adsorbed by the composite material increases. When the initial concentration of As (V) is 20 mg.L-1When the composite material is used, the adsorption capacity of the composite material to As (V) can reach 19 mg.g-1。
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (6)

1. The preparation method of the goethite/carboxylated cellulose nanocrystalline composite material for removing the heavy metal ions is characterized by comprising the following steps of:
(1) dispersing 32.5g of 3.2 wt% carboxylated cellulose nanocrystals into 67.5g of deionized water at room temperature, and magnetically stirring for 20min to form 1 wt% carboxylated cellulose nanocrystal dispersion;
(2) adding Fe (NO) to the dispersion obtained in the step (1)3)3·9H2O, magnetically stirring for 8 hours at room temperature to obtain Fe3+A carboxylated cellulose nanocrystal complexing mixed solution;
(3) adding a NaOH solution with the concentration of 5M into the mixed solution obtained in the step (2) while stirring to adjust the pH of the mixed solution, and continuously stirring for 30 s;
(4) and (4) transferring the mixed solution obtained in the step (3) to a hydrothermal reaction kettle, sealing, placing the hydrothermal reaction kettle in an oven for hydrothermal reaction, washing the obtained product after the reaction is finished, and placing the product in a vacuum drying oven for drying at 50 ℃ for 12 hours to finally obtain the goethite/carboxylated cellulose nanocrystalline composite material.
2. The method for preparing goethite/carboxylated cellulose nanocrystal composite material for removing heavy metal ions according to claim 1, wherein the Fe (NO) added in the step (2)3)3·9H2The mass of O is 0-10 g.
3. The method for preparing goethite/carboxylated cellulose nanocrystal composite material for removing heavy metal ions according to claim 1, wherein the pH of the mixed solution is adjusted to pH >13 in the step (3).
4. The method for preparing goethite/carboxylated cellulose nanocrystal composite material for removing heavy metal ions according to claim 1, wherein the hydrothermal reaction condition in the step (4) is 70 ℃ for 12 hours.
5. The preparation method of the goethite/carboxylated cellulose nanocrystalline composite material for removing the heavy metal ions according to claim 1, characterized in that after the reaction in the step (4) is finished, the obtained product is washed by deionized water repeatedly until the product is neutral, and then is washed by absolute ethyl alcohol for 2-3 times.
6. The method for preparing the goethite/carboxylated cellulose nanocrystal composite material for removing the heavy metal ions As claimed in claim 1, wherein the goethite/carboxylated cellulose nanocrystal composite material is capable of removing one or more heavy metal ions of Pb (II), Cd (II) or As (V) in heavy metal wastewater.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113428930A (en) * 2021-06-30 2021-09-24 浙江理工大学 Organic wastewater treatment method based on high-performance polyaniline aerogel
CN115487779A (en) * 2022-06-01 2022-12-20 同济大学 Preparation method of ferrous ion/cellulose nanocrystal/sodium alginate composite material and application of composite material in adsorption of tetracycline
CN116983950A (en) * 2023-05-23 2023-11-03 南京理工大学 MoS (MoS) 2 Fh composite material and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1559664A (en) * 2004-03-02 2005-01-05 武汉理工大学 Preparation of bacteria mineralized nanometer needle iron ore and its application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1559664A (en) * 2004-03-02 2005-01-05 武汉理工大学 Preparation of bacteria mineralized nanometer needle iron ore and its application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MING-GUO MA等: "Nanocomposites of cellulose/iron oxide: influence of synthesis conditions on their morphological behavior and thermal stability", 《MATERIALS SCIENCE AND ENGINEERING》 *
张伟等: "针铁矿＠纳米纤维素杂化纤维膜的制备及其水处理应用研究", 《2016年全国高分子材料科学与工程研讨会》 *

Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN113428930A (en) * 2021-06-30 2021-09-24 浙江理工大学 Organic wastewater treatment method based on high-performance polyaniline aerogel
CN115487779A (en) * 2022-06-01 2022-12-20 同济大学 Preparation method of ferrous ion/cellulose nanocrystal/sodium alginate composite material and application of composite material in adsorption of tetracycline
CN115487779B (en) * 2022-06-01 2023-07-28 同济大学 Preparation method of ferrous ion/cellulose nanocrystal/sodium alginate composite material and application of ferrous ion/cellulose nanocrystal/sodium alginate composite material in adsorption of tetracycline
CN116983950A (en) * 2023-05-23 2023-11-03 南京理工大学 MoS (MoS) 2 Fh composite material and preparation method and application thereof
CN116983950B (en) * 2023-05-23 2024-03-08 南京理工大学 MoS (MoS) 2 Fh composite material and preparation method and application thereof

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