ZINC ALUMINUM SILICATE/GRANULAR RED MUD COMPOSITE MATERIAL OF ZN2+-MODIFIED INDUSTRIAL WASTE RED MUD, PREPARATION METHOD AND APPLICATION THEREOF

Abstract

A zinc aluminium silicate nanoparticles/granular red mud (ZAS/GRM) composite material of Zn.sup.2+-modified industrial waste red mud and a preparation method and application thereof are disclosed, belonging to the technical field of adsorbent preparation. The industrial waste red mud is used as a raw material to prepare Zn.sup.2+-modified red mud for ZAS/GRM adsorbent.

Claims

1. A preparation method of a ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud, comprising following steps: S1, adding red mud, fly ash, a binder and a pore-forming agent into water for mixing, then carrying out artificial granulation to obtain GRM, and then carrying out air drying and roasting on the GRM to obtain porous GRM particles; and S2, immersing the porous GRM particles into a solution containing Zn.sup.2+, stirring, filtering and drying to obtain a zinc aluminum silicate/granular red mud adsorbent, a ZAS/GRM adsorbent, then obtaining a ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud by subjecting the ZAS/GRM adsorbent to roasting treatment.

2. The preparation method of the ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud according to claim 1, wherein in the S1, a particle size of the GRM is 5-10 mm; a duration of the air drying is 10-48 h; and technological parameters of the roasting are: preheating at 573-973 K for 0.1-2 h, and baking at 873K-1773K for 20-90 min.

3. The preparation method of the ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud according to claim 1, wherein in the S1, the solution containing Zn.sup.2+ is a ZnCl.sub.2, ZnSO.sub.4 or ZnCO.sub.3 solution, and a concentration of the solution containing Zn.sup.2+ is 0.10-0.30 mol.Math.L.sup.1.

4. The preparation method of the ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud according to claim 1, wherein in the S2, a dosage ratio of the porous GRM particles to the solution containing Zn.sup.2+ is (1.0-15) g:(20-100) mL.

5. The preparation method of the ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud according to claim 1, wherein in the S2, the stirring is continued for 10 to 48 h at a speed of 200 to 900 rpm; and a temperature for the drying is 333-600 K.

6. The preparation method of the ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud according to claim 1, wherein in the S2, a technological parameter of the roasting treatment is: roasting at 673-973 K for 1-5 h.

7. A ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud prepared by the preparation method of the ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG. 1 shows the elemental content of the ZAS/GRM adsorbent.

[0027] FIG. 2 shows the leaching concentration of heavy metal ions in ZAS/GRM composite in Embodiment 4.

[0028] FIG. 3A shows the N.sub.2 adsorption-desorption isotherms of porous GRM particles and ZAS/GRM adsorbent in Embodiment 4.

[0029] FIG. 3B shows the pore size distribution curves of porous GRM particles and ZAS/GRM adsorbent in Embodiment 4.

[0030] FIG. 4 illustrates a color comparison of ZAS/GRM composite before and after CR adsorption in Embodiment 4.

[0031] FIG. 5 is a comparison of the effects of porous GRM particles and ZAS/GRM adsorbent on CR removal in Embodiment 4.

[0032] FIG. 6A is a Transmission Electron Microscope (TEM) image of ZAS/GRM adsorbent in Embodiment 4.

[0033] FIG. 6B shows the high resolution TEM image of ZAS/GRM adsorbent in Embodiment 4.

[0034] FIG. 6C shows the energy-dispersive spectroscopy (EDS) mapping of ZAS/GRM adsorbent in Embodiment 4.

[0035] FIG. 7 is a process illustrating the preparation method of ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] In order to make those skilled in the art understand the characteristics and effects of the present disclosure, the following is a general description and definition of terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in this disclosure are the ordinary meanings understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0037] The theories or mechanisms described and disclosed herein, whether right or wrong, should not limit the scope of the present disclosure in any way, that is, the contents of the present disclosure may be implemented without being limited by any particular theory or mechanism.

[0038] In this disclosure, all characteristics defined in the form of numerical range or percentage range, such as numerical value, quantity, content and concentration, are only for simplicity and convenience. Accordingly, the description of numerical range or percentage range shall be deemed to have covered and specifically disclosed all possible sub-ranges and individual values within the range (including integers and fractions).

[0039] In this disclosure, unless otherwise specified, the words containing, including, comprising, having or similar words cover the meanings of consisting of and mainly consisting of. For example, A contains a covers the meanings of A contains a and others and A only contains a.

[0040] Here, for the sake of brevity, not all possible combinations of various technical features in various implementations or embodiments are described. Therefore, as long as there is no contradiction in the combination of these technical features, each technical feature in each implementation or embodiment may be combined arbitrarily, and all possible combinations should be considered as the scope specified by this specification.

[0041] The disclosure provides a preparation method of a ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud, including the following steps as shown in FIG. 7:

[0042] S1, adding red mud, fly ash, a binder and a pore-forming agent into water for mixing, then carrying out artificial granulation to obtain GRM, and then carrying out air drying and roasting on the GRM to obtain porous GRM particles; and

[0043] S2, immersing the porous GRM particles into a solution containing Zn.sup.2+, stirring, filtering and drying to obtain a ZAS/GRM adsorbent, then obtaining a ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud by subjecting the ZAS/GRM adsorbent to roasting treatment.

[0044] The present disclosure will be further elaborated with specific embodiments. It should be understood that these embodiments are only used to illustrate the disclosure and are not used to limit the scope of the disclosure. In addition, it should be understood that after reading the present disclosure, those skilled in the art may make various changes or modifications to the present disclosure, and these equivalent forms also fall within the scope defined by the appended claims of this disclosure.

[0045] Conventional instruments and equipment in the technical field are used in the following embodiments. The experimental methods without specific conditions in the following embodiments usually follow the conventional conditions or the conditions suggested by the manufacturers. Unless otherwise specified, all the raw materials used in the following embodiments are commercially available products, and their specifications are conventional in this technical field. In the specification of the present disclosure and the following embodiments, unless otherwise specified, % means weight percentage, part means weight part, and a proportion stands for a weight ratio.

Embodiment 1

[0046] A preparation method of a zinc aluminum silicate/granular red mud (ZAS/GRM) composite material of Zn.sup.2+-modified industrial waste red mud, including the following steps:

[0047] S1, fully grinding red mud (RM), fly ash (FA), NaHCO.sub.3 and C.sub.6H.sub.12O.sub.6 (binder) as raw materials, screening with a 100-mesh sieve, and then mixing under the mass ratio of RM:FA:NaHCO.sub.3:C.sub.6H.sub.12O.sub.6 of 70:10:10:10 to obtain powder A; subsequently, adding 20 mL deionized water to the obtained powder A to form a mud cake, and obtaining GRM with a particle size of 5 mm by artificial granulation; then, air-drying GRM for 24 h, followed by preheating at 273 K for 0.1 h and baking at 873 K for 20 min, and finally preparing the porous GRM particles; and

[0048] S2, preparing 20 mL of 0.10 mol.Math.L.sup.1 aqueous solution of ZnCl.sub.2, then immersing 1 g of porous GRM particles in the aqueous solution of ZnCl.sub.2 while continuously stirring at 200 rpm, and after 10 h, filtering and drying at 273 K to obtain the ZAS/GRM adsorbent; before the adsorption experiment, treating the ZAS/CRM adsorbent at 600 K for 1 h to obtain the Zn.sup.2+-modified industrial waste red mud adsorbent.

Embodiment 2

[0049] A preparation method of ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud, including the following steps:

[0050] S1, fully grinding red mud (RM), fly ash (FA), NaHCO.sub.3 and C.sub.6H.sub.12O.sub.6 (binder) as raw materials, screening with a 300-mesh sieve, and then mixing under the mass ratio of RM:FA:NaHCO.sub.3:C.sub.6H.sub.12O.sub.6 of 70:10:10:10 to obtain powder A; subsequently, adding 200 mL deionized water to the obtained powder A to form a mud cake, and obtaining GRM with a particle size of 7 mm by artificial granulation; then, air-drying GRM for 10 h, followed by preheating at 573 K for 1.5 h and baking at 973 K for 20 min, and finally preparing the porous GRM particles; and

[0051] S2, preparing 50 mL of 0.17 mol.Math.L.sup.1 aqueous solution of ZnCl.sub.2, then immersing 8 g of porous GRM particles in the aqueous solution of ZnCl.sub.2 while continuously stirring at 900 rpm, and after 48 h, filtering and drying at 273 K to obtain the ZAS/GRM adsorbent; before the adsorption experiment, treating the ZAS/CRM adsorbent at 600 K for 5 h to obtain the Zn.sup.2+-modified industrial waste red mud adsorbent.

Embodiment 3

[0052] A preparation method of ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud, including the following steps:

[0053] S1, fully grinding red mud (RM), fly ash (FA), NaHCO.sub.3 and C.sub.6H.sub.12O.sub.6 (binder) as raw materials, screening with a 100-mesh sieve, and then mixing under the mass ratio of RM:FA:NaHCO.sub.3:C.sub.6H.sub.12O.sub.6 of 75:10:5:10 to obtain powder A; subsequently, adding 100 mL deionized water to the obtained powder A to form a mud cake, and obtaining GRM with a particle size of 6 mm by artificial granulation; then, air-drying GRM for 36 h, followed by preheating at 673 K for 2 h and baking at 1173 K for 60 min, and finally preparing the porous GRM particles; and

[0054] S2, preparing 80 mL of 0.3 mol.Math.L.sup.1 aqueous solution of ZnCl.sub.2, then immersing 10 g of porous GRM particles in the aqueous solution of ZnCl.sub.2 while continuously stirring at 600 rpm, and after 48 h, filtering and drying at 500 K to obtain the ZAS/GRM adsorbent; before the adsorption experiment, treating the ZAS/CRM adsorbent at 773 K for 2.5 h to obtain the Zn.sup.2+-modified industrial waste red mud adsorbent.

Embodiment 4

[0055] A preparation method of ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud, including the following steps:

[0056] S1, fully grinding red mud (RM), fly ash (FA), NaHCO.sub.3 and C.sub.6H.sub.12O.sub.6 (binder) as raw materials, screening with a 100-mesh sieve, and then mixing under the mass ratio of RM:FA:NaHCO.sub.3:C.sub.6H.sub.12O.sub.6 of 75:10:5:10 to obtain powder A; subsequently, adding 100 mL deionized water to the obtained powder A to form a mud cake, and obtaining GRM with a particle size of 7 mm by artificial granulation; then, air-drying GRM for 24 h, followed by preheating at 773 K for 0.5 h and baking at 1173 K for 20 min, and finally preparing the porous GRM particles; and

[0057] S2, preparing 150 mL of 0.15 mol.Math.L.sup.1 aqueous solution of ZnCl.sub.2, then immersing 12 g of porous GRM particles in the aqueous solution of ZnCl.sub.2 while continuously stirring at 300 rpm, and after 24 h, filtering and drying at 333 K to obtain the ZAS/GRM adsorbent; before the adsorption experiment, treating the ZAS/CRM adsorbent at 773 K for 3 h to obtain the Zn.sup.2+-modified industrial waste red mud adsorbent.

Embodiment 5

[0058] A preparation method of ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud, including the following steps:

[0059] S1, fully grinding red mud (RM), fly ash (FA), NaHCO.sub.3 and C.sub.6H.sub.12O.sub.6 (binder) as raw materials, screening with a 100-mesh sieve, and then mixing under the mass ratio of RM:FA:NaHCO.sub.3:C.sub.6H.sub.12O.sub.6 of 75:10:5:10 to obtain powder A; subsequently, adding 150 mL deionized water to the obtained powder A to form a mud cake, and obtaining GRM with a particle size of 7 mm by artificial granulation; then, air-drying GRM for 42 h, followed by preheating at 773 K for 1.5 h and baking at 1073 K for 50 min, and finally preparing the porous GRM particles; and

[0060] S2, preparing 160 mL of 0.25 mol.Math.L.sup.1 aqueous solution of ZnCl.sub.2, then immersing 13 g of porous GRM particles in the aqueous solution of ZnCl.sub.2 while continuously stirring at 800 rpm, and after 48 h, filtering and drying at 600 K to obtain the ZAS/GRM adsorbent; before the adsorption experiment, treating the ZAS/CRM adsorbent at 873 K for 5 h to obtain the Zn.sup.2+-modified industrial waste red mud adsorbent.

Embodiment 6

[0061] A preparation method of ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud, including the following steps:

[0062] S1, fully grinding red mud (RM), fly ash (FA), NaHCO.sub.3 and C.sub.6H.sub.12O.sub.6 (binder) as raw materials, screening with a 100-mesh sieve, and then mixing under the mass ratio of RM:FA:NaHCO.sub.3:C.sub.6H.sub.12O.sub.6 of 75:10:5:10 to obtain powder A; subsequently, adding 180 mL deionized water to the obtained powder A to form a mud cake, and obtaining GRM with a particle size of 6 mm by artificial granulation; then, air-drying GRM for 30 h, followed by preheating at 873 K for 1 h and baking at 973 K for 80 min, and finally preparing the porous GRM particles; and

[0063] S2, preparing 180 mL of 0.15 mol.Math.L.sup.1 aqueous solution of ZnCl.sub.2, then immersing 14 g of porous GRM particles in the aqueous solution of ZnCl.sub.2 while continuously stirring at 750 rpm, and after 40 h, filtering and drying at 573 K to obtain the ZAS/GRM adsorbent; before the adsorption experiment, treating the ZAS/CRM adsorbent at 673 K for 4 h to obtain the Zn.sup.2+-modified industrial waste red mud adsorbent.

Embodiment 7

[0064] A preparation method of ZAS/GRM composite material of Zn.sup.2+-modified industrial waste red mud, including the following steps:

[0065] S1, fully grinding red mud (RM), fly ash (FA), NaHCO.sub.3 and C.sub.6H.sub.12O.sub.6 (binder) as raw materials, screening with a 300-mesh sieve, and then mixing under the mass ratio of RM:FA:NaHCO.sub.3:C.sub.6H.sub.12O.sub.6 of 80:5:5:10 to obtain powder A; subsequently, adding 200 mL deionized water to the obtained powder A to form a mud cake, and obtaining GRM with a particle size of 7 mm by artificial granulation; then, air-drying GRM for 48 h, followed by preheating at 973 K for 2 h and baking at 1773 K for 90 min, and finally preparing the porous GRM particles; and

[0066] S2, preparing 200 mL of 0.3 mol.Math.L.sup.1 aqueous solution of ZnCl.sub.2, then immersing 15 g of porous GRM particles in the aqueous solution of ZnCl.sub.2 while continuously stirring at 900 rpm, and after 48 h, filtering and drying at 600 K to obtain the ZAS/GRM adsorbent; before the adsorption experiment, treating the ZAS/CRM adsorbent at 973 K for 5 h to obtain the Zn.sup.2+-modified industrial waste red mud adsorbent.

[0067] FIG. 1 shows the elemental content of the ZAS/GRM adsorbent. It can be seen from the FIG. 1 that the content ratios of 27.54%, 7.08%, 2.36%, and 29.86% of Zn, Al, Si, and O, respectively, were distributed on the ZAS/CRM adsorbent.

[0068] FIG. 2 shows the leaching concentration of heavy metal ions in ZAS/GRM composite in Embodiment 4. From the FIG. 2, it is observed that the concentration of heavy metal elements As, Cd and Pb in the impregnation solution is lower than the wastewater discharge standard. In addition, compared with 0 mol.Math.L.sup.1 ZnCl.sub.2 (aq), the Na.sup.+ content in 0.10, 0.15 and 0.20 mol.Math.L.sup.1 ZnCl.sub.2 are sharply increased, indicating that there is ion exchange between Zn.sup.2+ of ZnCl.sub.2 and Na.sup.+ of GRM.

[0069] FIG. 3A-FIG. 3B show the N.sub.2 adsorption-desorption curves of different materials, with obvious H3 hysteresis loops, indicating that GRM and ZAS/GRM adsorbents have mesoporous properties. After Zn.sup.2+ modification, the specific surface area of porous ZAS/GRM adsorbent are increased from 2.8911 m.sub.2.Math.g.sup.1 to 12.0333 m.sub.2.Math.g.sup.1. The ZAS/GRM adsorbent with a 6-fold increase in specific surface area provides more active sites for organic pollutants, thus greatly improving its adsorption behavior. FIG. 3B shows further characterized mesoporous distribution of GRM and ZAS/GRM adsorbents. The average pore size of ZAS/GRM adsorbent is 25.412 nm, while that of GRM adsorbent is 41.918 nm. The decrease of pore size is attributed to the loading of ZAS nanoparticles on GRM surface.

[0070] FIG. 4 shows the color comparison of ZAS/GRM composite before (a yellow CR solution, which appears relatively dark in the black-white FIG. 4) and after (a clarified solution, presented as a clearer and more transparent appearance in the black-white FIG. 4) absorbing CR in Embodiment 4. From the FIG. 4, it is observed that CR is well absorbed on ZAS/GRM composite, achieving the purification effect.

[0071] FIG. 5 shows a comparison of the effects of porous GRM particles and ZAS/GRM adsorbent on CR removal in Embodiment 4. From the FIG. 5, it may be seen that ZAS/GRM adsorbent achieves efficient solid-liquid separation, thus significantly reducing the loss of adsorbent quality and secondary pollution to the environment during the separation process.

[0072] FIG. 6A-FIG. 6C illustrate the performance characterization diagram of ZAS nanoparticles on the surface of ZAS/GRM adsorbent in Embodiment 4. From FIG. 6A-FIG. 6C, it is observed that ZAS nanoparticles are uniformly distributed on the surface of ZAS/GRM adsorbent, and the analysis results of energy dispersive spectrometer show that Zn, Al, Si and O are uniformly distributed on the surface of ZAS/GRM adsorbent, which indicates that ZnAlSiO material is successfully generated on the surface of GRM.

[0073] The above contents are only for explaining the technical idea of the present disclosure, and may not be used to limit the protection scope of the present disclosure. Any changes made on the basis of the technical scheme according to the technical idea proposed by the present disclosure shall fall within the protection scope defined by the claims of the present disclosure.