CN114713208B - Preparation method and application of modified hydrotalcite-based aluminum magnesium oxide - Google Patents
Preparation method and application of modified hydrotalcite-based aluminum magnesium oxide Download PDFInfo
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- CN114713208B CN114713208B CN202210533282.6A CN202210533282A CN114713208B CN 114713208 B CN114713208 B CN 114713208B CN 202210533282 A CN202210533282 A CN 202210533282A CN 114713208 B CN114713208 B CN 114713208B
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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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- 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
- B01J20/06—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
- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
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Abstract
The invention belongs to the field of organic dye wastewater treatment, and relates to a preparation method and application of a modified hydrotalcite-based magnesium aluminum oxide. The preparation method disclosed by the invention takes hydrotalcite as a raw material, prepares the magnesium oxide adsorbent with high adsorption activity to anionic dye through solvothermal reaction and high-temperature roasting, and the surface of the magnesium oxide adsorbent has a large amount of sheet structures. The invention increases the density of the adsorption active sites and improves the adsorption activity by regulating the surface morphology of the magnesium oxide, and has the advantages of cheap and easily obtained raw materials, mild reaction conditions, simple synthesis process and the like, thereby having good economic and social values.
Description
Technical Field
The invention relates to the technical field of organic dye wastewater treatment, in particular to a preparation method and application of a modified hydrotalcite-based aluminum magnesium oxide.
Background
With the development of textile, plastic and leather industries, a large amount of wastewater is discharged into the environment, which poses serious threats to human survival. Many techniques such as photodegradation, adsorption, biological treatment, chemical coagulation, etc. have been developed to remove organic dyes from wastewater, and the adsorption method is considered to be the most effective and economical method.
Hydrotalcite is a Layered Double Hydroxide (LDH) and is composed of positively charged host layered plates, anions filled between the layered plates, and water molecules. The hydrotalcite has laminated metal cation layers and interlayerThe characteristics of adjustable distance and variability and interlayer anion exchangeability, and the advantages of no toxicity, convenient preparation, low cost and the like are widely concerned in the treatment of toxic wastewater. Li et al prepared Mg (OH) by phase transfer in an autoclave 2 The material is used as a precursor to prepare magnesium oxide with a nano layered structure, and the adsorption performance of the magnesium oxide on Congo red dye is 2650mg/g. Chinese patent CN201611147020.7 uses magnesium nitrate and sodium carbonate as raw materials, uses sodium silicate as dispersant to prepare high-capacity magnesium oxide adsorbent, has adsorption activity of 3200mg/g on Congo red, and lays a foundation for developing and designing high-activity adsorbent for dye wastewater treatment technology.
In view of the above, those skilled in the art need to develop an adsorbent with stable adsorption performance, low cost of raw materials, simple preparation process and high adsorption capacity to meet the actual needs.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a modified hydrotalcite-based magnesium aluminum oxide and application of a dye adsorbent, and providing a preparation method of a modified hydrotalcite-based magnesium aluminum oxide adsorbent with large adsorption capacity and good regeneration cycle stability.
In order to solve the technical problems, the invention adopts the following technical scheme: adding a certain amount of self-made or commercially available magnesium-aluminum hydrotalcite into a proper amount of mixed solvent, uniformly stirring, adjusting the pH value, carrying out solvent heat treatment in a sealed reactor, filtering, washing, drying and roasting a product after reaction at high temperature to synthesize the adsorbent having adsorption performance on anionic dye.
Further, the mixed solvent is any one or a mixture of any several of ethanol, ethylene glycol, propanol, butanol and water.
Further, adjusting the pH value to be 9-11, and taking sodium hydroxide, potassium hydroxide and ammonia water as alkali sources.
Further, the solvent thermal reaction temperature is 120 to 180 ℃, and the reaction time is 2 to 10 hours.
Further, the sealed reactor is a standing or stirring reactor.
Further, the magnesium-aluminum molar ratio of the magnesium-aluminum hydrotalcite is 2.0-4.0.
The preparation method of the modified hydrotalcite-based aluminum magnesium oxide comprises the following steps:
(1) Adding a certain amount of magnalium hydrotalcite into a proper amount of mixed solvent, stirring at room temperature for 30 minutes until the mixture is uniform, adjusting the pH value to 9-11 with alkali liquor, and continuously stirring the mixture for 20 minutes.
(2) And (2) carrying out solvothermal treatment in a sealed reactor, wherein the reaction temperature is 120 to 180 ℃, the reaction time is 2 to 10 hours, and a reaction product is filtered, washed by water or ethanol and dried for 6 to 12 hours at the temperature of 80 ℃.
(3) And (3) roasting the reaction product in a muffle furnace at a high temperature of 500-650 ℃ for 2-6 hours, and preparing the modified hydrotalcite-based magnesium aluminum oxide adsorbent into the adsorbent which has adsorption performance on anionic dye.
The invention has the beneficial effects that:
1. the layered magnesium-aluminum oxide prepared by using the hydrotalcite as the precursor has the characteristics of large specific surface area and high isoelectric point, is beneficial to the adsorption of the layered magnesium-aluminum oxide on anionic dye, and in addition, the surface of the modified magnesium-aluminum oxide has a large number of nano wafers (about 150 nanometers), so that the basic strength and the basic number of magnesium oxide are increased due to the existence of crystal boundaries, and the adsorption activity of the adsorbent is greatly improved.
2. The modified magnesium-aluminum oxide adsorbent has pore channels (50-100 nanometers) formed by the staggered nano wafers on the surface, reduces the diffusion resistance of the adsorbate, and is favorable for quickly adsorbing the dye in the wastewater.
3. The preparation method has low cost and mild synthesis conditions, is beneficial to industrial scale popularization, and lays a foundation for treating dye wastewater by using the modified adsorbent.
Drawings
FIG. 1 is a scanning electron micrograph of hydrotalcite as a raw material in example 3;
FIG. 2 is a scanning electron micrograph of the modified hydrotalcite-based magnesium aluminum oxide prepared in example 3;
FIG. 3 is a TEM image of the modified hydrotalcite-based magnesium aluminum oxide prepared in example 3;
FIG. 4 is a line graph of the equilibrium dye capacity versus time for the modified hydrotalcite-based magnesium aluminum oxide prepared in example 3.
Detailed Description
The present invention will now be described in detail with reference to examples, which are provided only for describing embodiments of the present invention and should not be construed as limiting the scope of the present invention. In the examples, the preparation and performance test were conducted under conventional conditions, and the reagents and instruments used were not indicated by the manufacturer, and were commercially available as conventional products.
Preparation of hydrotalcite
Proper molar ratio of Mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in 60mL of deionized water, uniformly stirring, adding a certain amount of urea, wherein the amount of the urea is 3.5 times of that of the metal ion substances, uniformly stirring, transferring the solution into a reaction kettle, reacting at 100 ℃ for 24 hours, naturally cooling, filtering, washing with water and ethanol, drying, and synthesizing the magnesium-aluminum hydrotalcite.
Example 1
Preparation of modified hydrotalcite-based magnesium aluminum oxide
Adding 0.2g of magnesium-aluminum hydrotalcite (the molar ratio of magnesium to aluminum is 2) into 40mL of ethanol, stirring for 30min, adjusting the pH value to 11, then transferring to a sealed reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 10h, naturally cooling, filtering to obtain a white product, washing, drying, roasting at 650 ℃ in a muffle furnace for 2h (the heating rate is 3 ℃/min), and thus obtaining the magnesium-aluminum oxide adsorbent which is named as LDO-1.
Example 2
Preparation of modified hydrotalcite-based magnesium aluminum oxide
Adding 0.5g of magnesium-aluminum hydrotalcite (the molar ratio of magnesium to aluminum is 3) into 40mL of butanol, stirring for 30min, adjusting the pH value to 10 by 5 percent by mass of NaOH solution, then transferring into a sealed reaction kettle, carrying out hydrothermal treatment at 130 ℃ for 3h, naturally cooling, filtering, washing the obtained white product, drying, and roasting at a high temperature of 500 ℃ in a muffle furnace for 10h (the heating rate is 10 ℃/min) to obtain the magnesium-aluminum oxide adsorbent, which is named as LDO-2.
Example 3
Preparation of modified hydrotalcite-based magnesium aluminum oxide
Adding 3.0g of magnesium-aluminum hydrotalcite (the molar ratio of magnesium to aluminum is 3) into 40mL of propanol, stirring for 30min, adjusting the pH value to 9.5, then transferring to a stirring sealed reaction kettle (the rotating speed is 150 r/min), carrying out hydrothermal treatment at 160 ℃ for 6h, naturally cooling, filtering, washing an obtained white product, drying, and roasting at 550 ℃ in a muffle furnace for 6h (the heating rate is 10 ℃/min) to obtain the magnesium-aluminum oxide adsorbent named as LDO-3.
Example 4
Preparation of modified hydrotalcite-based magnesium aluminum oxide
Adding 5.0g of magnesium-aluminum hydrotalcite (the molar ratio of magnesium to aluminum is 4) into 40mL of ethylene glycol, stirring for 30min, adjusting the pH value to 9, then transferring to a sealed reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 2h, naturally cooling, filtering to obtain a white product, washing, drying, and roasting at a high temperature of 500 ℃ in a muffle furnace for 2h (the heating rate is 5 ℃/min) to obtain the magnesium-aluminum oxide adsorbent named as LDO-4.
Example 5
Preparation of modified hydrotalcite-based magnesium aluminum oxide
Adding 5.0g of magnesium-aluminum hydrotalcite (the molar ratio of magnesium to aluminum is 3.5) into 40mL of propanol and water (1).
Example 6
Preparation of modified hydrotalcite-based magnesium aluminum oxide
Adding 8.0g of magnesium-aluminum hydrotalcite (the molar ratio of magnesium to aluminum is 3) into 40mL of ethanol and water (1).
Note: the magnesium aluminum oxide adsorbents obtained in examples 1 to 6 were subjected to an adsorbent activity evaluation test, and the test results are shown in table 1
The method for evaluating the activity of the adsorbent comprises the following steps:
adding the above adsorbents into the same beaker containing 25mL of Congo Red (CR) dye solution (60-2000 mg/L, pH = 5-12) with a certain mass concentration, stirring at 100rpm on a magnetic stirrer to reach equilibrium, centrifuging the supernatant, detecting with a spectrophotometer, and determining the equilibrium dye capacity (q) from the following equation (1) e ）。
q e =（c 0 -c e ）×v/m (1)
Wherein, c 0 And c e Respectively the initial concentration of the dye and the concentration of the dye at the time t, wherein the unit is mol/L;
v is the volume of the solution in L;
m is the mass of the added adsorbent and the unit is g;
table 1 results of adsorption activity test of modified hydrotalcite-based magnesium aluminum oxide to congo red of examples 1 to 6
| Name of adsorbent | LDO-1 | LDO-2 | LDO-3 | LDO-4 | LDO-5 | LDO-6 | LDO (reference) |
| Adsorption Capacity (mg/g) | 2540 | 3958 | 6235 | 3756 | 4710 | 5700 | 1560 |
It should be understood that the examples and embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the present disclosure, and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this disclosure.
Claims (8)
1. A preparation method of modified hydrotalcite-based aluminum magnesium oxide is characterized by comprising the following steps: adding hydrotalcite into a solvent, stirring uniformly, adjusting the pH value by using an alkali source, carrying out solvothermal treatment in a sealed reactor, wherein the solvothermal reaction temperature is 120-180 ℃, the reaction time is 2-10 hours, and filtering, washing, drying and roasting a product after the reaction to obtain the hydrotalcite.
2. The process for preparing a modified hydrotalcite-based magnesium aluminum oxide according to claim 1, wherein: the hydrotalcite is magnesium-aluminum hydrotalcite with the magnesium-aluminum molar ratio of 2.0-4.0.
3. The process for preparing a modified hydrotalcite-based magnesium aluminum oxide according to claim 1, wherein: the solvent is any one or a mixture of any more of ethanol, ethylene glycol, propanol, butanol and water, and the ratio of the volume of the solvent to the mass of the hydrotalcite is 5-200mL/g.
4. The process for preparing a modified hydrotalcite-based magnesium aluminum oxide according to claim 1, wherein: the alkali source is ammonia water or a sodium hydroxide solution, and the pH value is adjusted to be 9 to 11.
5. The process for preparing a modified hydrotalcite-based magnesium aluminum oxide according to claim 1, wherein: the sealed reactor is a reactor which is kept stand or provided with a stirring device.
6. The process for preparing a modified hydrotalcite-based magnesium aluminum oxide according to claim 1, wherein: the high-temperature roasting temperature is 500 to 650 ℃, and the heating rate is 3 to 15 ℃/min.
7. A modified hydrotalcite-based magnesium aluminum oxide prepared by the preparation method of the modified hydrotalcite-based magnesium aluminum oxide according to any one of claims 1 to 6.
8. Use of the modified hydrotalcite based magnesium aluminium oxide according to claim 7 as an adsorbent for adsorption of anionic dyes.
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| CN101798123A (en) * | 2010-03-26 | 2010-08-11 | 浙江工业大学 | Application of bimetal composite oxide in adsorbing acid violet 90 in dye wastewater |
| JP2017171547A (en) * | 2016-03-24 | 2017-09-28 | 協和化学工業株式会社 | Novel hydrotalcite particle having hierarchical structure |
| CN108927169B (en) * | 2018-08-17 | 2021-02-09 | 太原理工大学 | Preparation method and application of hydrotalcite-based CoMnFe composite metal oxide denitration catalyst |
| CN110496589B (en) * | 2019-08-27 | 2020-11-10 | 西安交通大学 | Hydrotalcite, preparation method thereof and application of hydrotalcite in PFOS (Perfluorooctane sulfonate) pollutant adsorption in water body |
| CN111298760A (en) * | 2020-03-16 | 2020-06-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of flower-like aluminum oxide-magnesium oxide composite adsorbent, product and application thereof |
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