CN111135794B - Alumina modified expanded graphite adsorbent and preparation method and application thereof - Google Patents
Alumina modified expanded graphite adsorbent and preparation method and application thereof Download PDFInfo
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- CN111135794B CN111135794B CN202010030206.4A CN202010030206A CN111135794B CN 111135794 B CN111135794 B CN 111135794B CN 202010030206 A CN202010030206 A CN 202010030206A CN 111135794 B CN111135794 B CN 111135794B
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Abstract
The inventionProvides an alumina modified expanded graphite adsorbent and a preparation method and application thereof, relating to the technical field of adsorbents. The preparation method of the alumina modified expanded graphite adsorbent comprises the steps of adding a dispersing agent into soluble aluminum salt and expanded graphite to obtain an aqueous solution A, then reacting the aqueous solution A with an alkaline substance, and activating to obtain the alumina modified expanded graphite adsorbent, wherein the dispersing agent comprises alcohols with carbon atoms of C1-C4, and because the dispersing agent has hydrogen bonds, the surface property of the expanded graphite can be improved and adsorption active sites can be increased by connecting hydroxide ions on the surface of the expanded graphite, and when the expanded graphite is soaked in the soluble aluminum salt, Al is added 3+ The loading effect in the pores of the expanded graphite is improved, the effective content of alumina in the modified expanded graphite can be effectively increased, and the adsorption performance of the alumina modified expanded graphite adsorbent is further improved. The invention also provides the alumina modified expanded graphite adsorbent and application thereof.
Description
Technical Field
The invention relates to the technical field of adsorbents, and particularly relates to an alumina modified expanded graphite adsorbent and a preparation method and application thereof.
Background
The expanded graphite is a porous material, is often used as an adsorbent and has attracted attention in the aspect of metal ion wastewater treatment, but the single use of the expanded graphite has certain limitation on application and cannot achieve a good adsorption effect. Alumina, especially gamma-Al 2 O 3 The composite material has the characteristics of low cost, wide source, high specific surface area, adjustable pore structure and pore size distribution, high mechanical strength and good thermal stability. Therefore, the expanded graphite can be modified by the alumina to prepare the adsorbent with excellent adsorption performance.
In the prior art, in the process of preparing the alumina modified expanded graphite, firstly, a precipitation method is adopted to obtain aluminum hydroxide/expanded graphite, then, the aluminum hydroxide/expanded graphite is filtered and washed by hot water, and then, the aluminum hydroxide is dehydrated and then treated to obtain the alumina modified expanded graphite. However, the following problems exist in the process:
(1) in the process of obtaining the aluminum hydroxide/expanded graphite by adopting a precipitation method, because the aluminum hydroxide has relatively poor dispersion performance and is easy to agglomerate, the load of the aluminum hydroxide in the gaps of the expanded graphite is influenced, so that the effective content of the aluminum oxide in the final aluminum oxide modified expanded graphite is lower, and the improvement of the adsorption performance of the aluminum oxide modified expanded graphite is not facilitated;
(2) part of aluminum hydroxide is lost in the process of cleaning with hot water after filtration, so that the Al content in the modified expanded graphite is far lower than the theoretical content.
Accordingly, the present invention is directed to solving at least one of the above problems.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of an alumina modified expanded graphite adsorbent, which can improve the loading effect of alumina in pores of expanded graphite, increase the effective content of alumina in the modified expanded graphite and improve the adsorption performance of the alumina modified expanded graphite adsorbent.
The second purpose of the invention is to provide an alumina modified expanded graphite adsorbent, which is prepared by adopting the preparation method of the alumina modified expanded graphite adsorbent.
The third purpose of the invention is to provide the application of the alumina modified expanded graphite adsorbent.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of an alumina modified expanded graphite adsorbent, which comprises the following steps:
providing an aqueous solution A containing a soluble aluminum salt, a dispersant and expanded graphite;
mixing the aqueous solution A and an alkaline substance to enable soluble aluminum salt to react with the alkaline substance to generate aluminum hydroxide, then separating, and activating the solid matter obtained by separation to obtain an alumina modified expanded graphite adsorbent;
wherein the dispersant comprises alcohols with carbon atoms of C1-C4.
Further, on the basis of the above technical solution of the present invention, the dispersant includes any one or a combination of at least two of methanol, ethanol, propanol or butanol, preferably ethanol;
preferably, the alkaline substance comprises any one of ammonia, sodium hydroxide or potassium hydroxide or a combination of at least two of them.
Further, on the basis of the technical scheme of the invention, the expansion volume of the expanded graphite in the aqueous solution A is 180-300 mL/g;
preferably, the mass ratio of the soluble aluminum salt, the dispersant and the expanded graphite in the aqueous solution A is (0.1-0.6): 10-30): 0.2-2, preferably (0.12-0.55): 12-28): 0.3-1.9;
preferably, the mass ratio of the alkaline substance to the soluble aluminum salt in the aqueous solution A is (20-40): (0.1-0.6).
Further, on the basis of the technical scheme, ammonia water is dripped into the aqueous solution A to react, and the dripping speed of the alkaline substance is 2-5 g/min;
preferably, the aqueous solution A is subjected to ultrasonic treatment after being reacted with an alkaline substance, then is kept stand, and then is separated;
preferably, the power of the ultrasound is 480-;
preferably, the activation temperature is 80-500 ℃ and the activation time is 3-10 h.
Further, on the basis of the above technical solution of the present invention, in the aqueous solution a, the soluble aluminum salt includes any one of aluminum nitrate, aluminum chloride or aluminum sulfate or a combination of at least two of them;
preferably, the expanded graphite comprises natural flake graphite.
Further, on the basis of the above technical solution of the present invention, the preparation method of the expanded graphite comprises the following steps:
reacting the flake graphite, the intercalation agent and the oxidant, then separating, drying the graphite intermediate product obtained by separation, and performing microwave expansion to obtain the expanded graphite.
Further, on the basis of the technical scheme of the invention, the mass ratio of the crystalline flake graphite to the intercalation agent to the oxidant is 1 (10-25) to (0.1-0.6);
preferably, the intercalating agent comprises nitric acid and phosphoric acid, and the volume ratio of nitric acid to phosphoric acid is 1: (0.5-3);
preferably, the oxidizing agent comprises potassium permanganate;
preferably, the reaction temperature is 30-60 ℃, and the reaction time is 10-80 min;
preferably, the power of the microwave expansion is 650-900W, and the time of the microwave expansion is 10-120 s.
Further, on the basis of the above technical scheme of the present invention, the preparation method of the alumina modified expanded graphite adsorbent comprises the following steps:
(a) providing an aqueous solution A containing soluble aluminium salt, ethanol and expanded graphite; wherein the mass ratio of the soluble aluminum salt, the ethanol and the expanded graphite is (0.1-0.6) to (10-30) to (0.2-2), and the expansion volume of the expanded graphite is 180-300 mL/g;
(b) and (2) dropwise adding ammonia water into the aqueous solution A to enable the soluble aluminum salt and the ammonia water to react to generate aluminum hydroxide, carrying out ultrasonic treatment after dropwise adding is finished, standing, then carrying out separation at 15-25 ℃, and activating the intermediate product of the modified expanded graphite obtained by separation at 80-500 ℃ for 3-10h to obtain the alumina modified expanded graphite adsorbent.
The invention also provides an alumina modified expanded graphite adsorbent, which is prepared by adopting the preparation method of the alumina modified expanded graphite adsorbent.
The invention also provides application of the alumina modified expanded graphite adsorbent in the field of water treatment.
Compared with the prior art, the alumina modified expanded graphite adsorbent and the preparation method and application thereof provided by the invention have the following technical effects:
(1) the invention provides a preparation method of an alumina modified expanded graphite adsorbent, which comprises the steps of adding a dispersing agent into soluble aluminum salt and expanded graphite to obtain an aqueous solution A, then reacting the aqueous solution A with an alkaline substance, and activating to obtain the alumina modified expanded graphite adsorbent, wherein the dispersing agent comprises alcohols with carbon atom numbers of C1-C4, and because the dispersing agent has hydrogen bonds, the surface property of the expanded graphite can be improved by connecting hydroxide ions on the surface of the expanded graphite, so that the adsorption active sites are increased, and when the expanded graphite is soaked in the soluble aluminum salt, Al 3+ The load effect in the pores of the expanded graphite is improved, and Al can be simultaneously enabled to be not caused to interact with powder 3+ The aluminum hydroxide generated with the alkaline substance is easy to filter, so thatThe aluminum hydroxide has good dispersibility, effectively inhibits the agglomeration of the aluminum hydroxide, is beneficial to forming ultrafine aluminum hydroxide particles and increases the surface area of the ultrafine aluminum hydroxide particles, so that the ultrafine aluminum hydroxide particles are well dispersed in the internal pores of the expanded graphite, the effective content of the aluminum oxide in the modified expanded graphite is increased, and the adsorption performance of the aluminum oxide modified expanded graphite adsorbent is improved.
(2) The invention provides an alumina modified expanded graphite adsorbent, which is prepared by adopting the preparation method of the alumina modified expanded graphite adsorbent. In view of the advantages of the preparation method of the alumina modified expanded graphite adsorbent, the effective content of alumina in the alumina modified expanded graphite adsorbent is higher, and meanwhile, the alumina modified expanded graphite adsorbent has good adsorption performance.
(3) The invention provides an application of an alumina modified expanded graphite adsorbent, which has good application in the field of water treatment in view of the advantages of the alumina modified expanded graphite adsorbent.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
According to a first aspect of the present invention, there is provided a process for the preparation of an alumina-modified expanded graphite adsorbent, comprising the steps of:
providing an aqueous solution A containing a soluble aluminum salt, a dispersant and expanded graphite;
mixing the aqueous solution A and an alkaline substance to enable soluble aluminum salt to react with the alkaline substance to generate aluminum hydroxide, then separating, and activating the solid matter obtained by separation to obtain an alumina modified expanded graphite adsorbent;
wherein the dispersant comprises C1-C4 alcohols.
Specifically, the expanded graphite has a loose structure, is porous and curved, has a large surface area and high surface energy, and has good adsorption performance. The source of the expanded graphite is not particularly limited, and may be made by itself or commercially available.
The soluble aluminium salt is mainly used for providing Al 3+ Using Al 3+ Reacting with alkaline substances to generate aluminum hydroxide precipitate, and then performing post-activation treatment to obtain the aluminum oxide. The activation treatment is mainly to make aluminum hydroxide generate aluminum oxide. The alumina has the characteristics of low cost, wide source, high specific surface area and mechanical strength, adjustable pore structure and pore size distribution and good thermal stability. The expanded graphite is compounded with alumina, and the obtained alumina modified expanded graphite adsorbent has more excellent adsorption performance.
The dispersant comprises C1-C4 alcohols. Because the dispersant has hydrogen bonds and can be connected with hydroxide ions on the surface of the expanded graphite, the surface property of the expanded graphite can be improved, adsorption active sites are increased, and when the expanded graphite is soaked in soluble aluminum salt, Al 3+ The load effect in the pores of the expanded graphite is improved, and Al can be simultaneously enabled to be not caused to interact with powder 3+ The aluminum hydroxide generated with alkaline substances is easy to filter, so that the dispersibility of the aluminum hydroxide is good, the agglomeration of the aluminum hydroxide is effectively inhibited, the formation of ultrafine aluminum hydroxide particles is facilitated, the surface area of the ultrafine aluminum hydroxide particles is increased, the ultrafine aluminum hydroxide particles are well dispersed in the internal pores of the expanded graphite, and the effective content of the aluminum oxide in the modified expanded graphite is increased. In addition, the dispersant has the advantages of small relative molecular mass, low cost, good initial dispersing effect and the like.
The invention provides a preparation method of an alumina modified expanded graphite adsorbent, which comprises the steps of adding a dispersing agent into soluble aluminum salt and expanded graphite to obtain an aqueous solution A, then reacting the aqueous solution A with an alkaline substance, and activating to obtain the alumina modified expanded graphite adsorbent, wherein the dispersing agent comprises alcohols with carbon atom numbers of C1-C4, and the surface property of the expanded graphite can be improved and adsorption active sites can be increased because the dispersing agent has hydrogen bonds and is connected with hydroxyl ions on the surfaceWith soluble aluminium salts, Al 3+ The loading effect in the pores of the expanded graphite is improved, the effective content of alumina in the expanded graphite can be effectively increased, and the adsorption performance of the alumina modified expanded graphite adsorbent is improved.
As an alternative embodiment of the present invention, the dispersant comprises any one of methanol, ethanol, propanol or butanol or a combination of at least two thereof, preferably ethanol.
As an alternative embodiment of the present invention, the alkaline substance includes any one of ammonia, sodium hydroxide or potassium hydroxide or a combination of at least two thereof, and preferably includes ammonia.
The dispersant is made to react with Al by limiting the specific kinds of the dispersant and the alkaline substance 3+ The aluminum hydroxide generated with the alkaline substance has better dispersion performance, and can improve the complexity of the aluminum hydroxide on the surface of the expanded graphite, thereby further improving the effective content of the aluminum oxide in the expanded graphite and the adsorbability of the aluminum oxide modified expanded graphite adsorbent.
Since the expanded graphite has a loose structure and is porous and curved, the expansion volume can be used to describe the degree of expansion of the expanded graphite. As an alternative embodiment of the present invention, the expanded volume of the expanded graphite in the aqueous solution A is 180-300 mL/g. It should be noted that "mL/g" means a volume per gram of the expanded graphite.
Typical but non-limiting expanded volumes of the expanded graphite are 180mL/g, 200mL/g, 210mL/g, 220mL/g, 240mL/g, 250mL/g, 260mL/g, 280mL/g, or 300 mL/g.
The expanded volume of the expanded graphite is related to the adsorption performance of the alumina-modified expanded graphite adsorbent. The expanded volume of the expanded graphite is limited, so that the obtained alumina modified expanded graphite adsorbent has better adsorption performance.
As an alternative embodiment of the present invention, the mass ratio of the soluble aluminum salt, the dispersant and the expanded graphite in the aqueous solution A is (0.1-0.6): (10-30): (0.2-2), preferably (0.12-0.55): (12-28): (0.3-1.9).
The mass ratio of the soluble aluminum salt to the dispersant to the expanded graphite in the aqueous solution A is 0.1:10:0.2, 0.2:10:0.2, 0.4:10:0.2, 0.5:10:0.2, 0.6:10:0.2, 0.1:15:0.2, 0.1:20:0.2, 0.1:25:0.2, 0.1:30:0.2, 0.1:15:0.5, 0.1:15:0.8, 0.1:15:1.0, 0.1:15:1.5, 0.1:15:2, 0.6:15:0.5, 0.6:15:0.8, 0.6:15:1.0, 0.6:15:1.5 or 0.6:15: 2.
As an alternative embodiment of the invention, the mass ratio of basic substance to soluble aluminium salt in aqueous solution A is (20-40): (0.1-0.6), typical but not limiting mass ratios of basic substance to soluble aluminium salt are 20:0.1, 25:0.1, 30:0.1, 35:0.1, 40:0.1, 20:0.2, 25:0.2, 30:0.2, 35:0.2, 40:0.2, 20:0.5, 25:0.5, 30:0.5, 35:0.5, 40:0.5, 20:0.6, 25:0.6, 30:0.6, 35:0.6 or 40: 0.6.
The soluble aluminum salt and the alkaline substance can be fully reacted to generate aluminum hydroxide by limiting the dosage ratio of the soluble aluminum salt, the dispersant, the expanded graphite and the alkaline substance, and the dispersant can fully realize the loading of the aluminum hydroxide on the expanded graphite, thereby improving the adsorption performance of the alumina modified expanded graphite adsorbent.
As an alternative embodiment of the present invention, the alkaline substance is added dropwise to the aqueous solution A to effect the reaction, the dropping rate of the alkaline substance being 2 to 5 g/min. Typical, but non-limiting, dropping rates of the basic substance are 2g/min, 2.5g/min, 3g/min, 3.5g/min, 4g/min, 4.5g/min, or 5 g/min.
The aluminum hydroxide is prepared by gradually and slowly adding alkaline substances into the aqueous solution A at a certain speed, and Al is added 3+ The effective contact area with alkaline substances can fully react with the alkaline substances, reduce the agglomeration of aluminum hydroxide, improve the dispersibility of the aluminum hydroxide and form stable Al (OH) 3 Expanded graphite.
As an optional embodiment of the invention, the aqueous solution A is subjected to ultrasonic treatment after being reacted with the alkaline substance, then is subjected to standing, and then is subjected to separation.
The aqueous solution A reacts with alkaline substances and then is subjected to ultrasound, and the ultrasound can further improve the dispersibility of the aluminum hydroxide and is beneficial to the preparation of nano-scale aluminum oxide. After ultrasonic treatment, the temperature of the mixture rises, and the mixture needs to be kept stand for a period of time to be cooled to normal temperature.
As an optional implementation manner of the invention, the power of the ultrasound is 480-; typical but non-limiting ultrasound has a power of 480W, 600W, 720W, or 900W, and typical but non-limiting ultrasound has a time of 0.5h, 1h, 1.5h, 2h, 2.5h, or 3 h.
As an alternative embodiment of the invention, the aqueous solution A is reacted with the alkaline substance, then ultrasonic treatment is carried out, then standing is carried out, and then separation is carried out at room temperature (15-25 ℃).
Separating at room temperature, avoiding the washing process with hot water, and reducing Al (OH) in pores of the expanded graphite 3 Loss of the catalyst. The separation means may be any of the conventional means such as suction filtration and the like.
As an alternative embodiment of the invention, the temperature of activation is 80-500 ℃ and the time of activation is 3-10 h. Typical but non-limiting activation temperatures are 80 deg.C, 100 deg.C, 120 deg.C, 150 deg.C, 180 deg.C, 200 deg.C, 220 deg.C, 250 deg.C, 280 deg.C, 300 deg.C, 320 deg.C, 350 deg.C, 380 deg.C, 400 deg.C, 420 deg.C, 450 deg.C, 480 deg.C or 500 deg.C.
By limiting the temperature and time of activation, Al (OH) is enabled 3 Al (OH) in expanded graphite 3 And dehydrating to generate a composite structure of the alumina and the expanded graphite, thereby obtaining the alumina modified expanded graphite adsorbent.
As an alternative embodiment of the present invention, in the aqueous solution a, the soluble aluminum salt includes any one of aluminum nitrate, aluminum chloride or aluminum sulfate or a combination of at least two of the two;
preferably, the expanded graphite comprises natural flake graphite.
There are various methods for preparing the expanded graphite. As an alternative embodiment of the present invention, the method for preparing the expanded graphite comprises the steps of:
reacting the flake graphite, the intercalation agent and the oxidant, then separating, drying the graphite intermediate product obtained by separation, and performing microwave expansion to obtain the expanded graphite.
The preparation method is a chemical oxidation intercalation method, and mainly utilizes an intercalation agent and an oxidizing agent to be inserted into the interlayer of graphite, and the expanded graphite is obtained through a series of treatments.
As an optional embodiment of the invention, the mass ratio of the crystalline flake graphite, the intercalation agent and the oxidizing agent is 1 (10-25) to 0.1-0.6; typical but non-limiting mass ratios of flake graphite, intercalant, and oxidant are 1:10:0.1, 1:10:0.2, 1:10:0.4, 1:10:0.5, 1:10:0.6, 1:15:0.1, 1:20:0.1, 1:25:0.1, 1:15:0.2, 1:20:0.2, 1:25:0.2, 1:15:0.4, 1:20:0.4, 1:25:0.4, 1:15:0.5, 1:20:0.5, 1:25:0.5, 1:15:0.6, 1:20:0.6, or 1:25: 0.6.
As an alternative embodiment of the invention, the intercalation agent comprises nitric acid and phosphoric acid, and the volume ratio of the nitric acid to the phosphoric acid is 1 (0.5-3);
preferably, the oxidizing agent comprises potassium permanganate;
as an optional embodiment of the invention, the reaction temperature is 30-60 ℃ and the reaction time is 10-80 min. Typical but not limiting reaction temperatures are 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, typical but not limiting reaction times are 10min, 20min, 30min, 40min, 50min, 60min, 70min or 80 min.
As an alternative embodiment of the invention, the power of the microwave expansion is 650- & ltwbr & gt 900W, and the time of the microwave expansion is 10-120 s. Typical but non-limiting microwave expansions have powers of 650W, 700W, 750W, 800W, 850W or 900W, and typical but non-limiting microwave expansions have times of 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s or 120 s.
The expanded graphite can have higher expansion volume by limiting the specific process parameters in the preparation method of the expanded graphite.
As an alternative embodiment of the present invention, the method for preparing the alumina-modified expanded graphite adsorbent comprises the steps of:
(a) providing an aqueous solution A containing soluble aluminum salt, ethanol and expanded graphite; wherein the mass ratio of the soluble aluminum salt, the ethanol and the expanded graphite is (0.1-0.6) to (10-30) to (0.2-2), and the expansion volume of the expanded graphite is 180-300 mL/g;
(b) and (3) dropwise adding ammonia water into the aqueous solution A to react, performing ultrasonic treatment after dropwise adding is finished, standing, then separating at 15-25 ℃, and activating the solid matter obtained by separation at 80-500 ℃ for 3-10h to obtain the alumina modified expanded graphite adsorbent.
Through further optimization of all steps and process parameters in the preparation method of the alumina modified expanded graphite adsorbent, the prepared alumina modified expanded graphite adsorbent has better adsorption performance.
According to the second aspect of the invention, the invention also provides an alumina modified expanded graphite adsorbent, which is prepared by adopting the preparation method of the alumina modified expanded graphite adsorbent.
In view of the advantages of the preparation method of the alumina modified expanded graphite adsorbent, the effective content of alumina in the alumina modified expanded graphite adsorbent is higher, and meanwhile, the alumina modified expanded graphite adsorbent has good adsorption performance.
According to a third aspect of the present invention, there is also provided the use of the above-described alumina-modified expanded graphite adsorbent in the field of water treatment.
In view of the advantages of the alumina modified expanded graphite adsorbent, the alumina modified expanded graphite adsorbent has good application in the field of water treatment.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
The embodiment provides a preparation method of an alumina modified expanded graphite adsorbent, which comprises the following steps:
(a) 0.1766g of Al (NO) was weighed out based on the mass ratio of alumina to expanded graphite of 0.06:1 3 ) 3 ·9H 2 Dissolving O and 25mL of absolute ethyl alcohol in a 500mL beaker, adding 125mL of distilled water and 0.4g of expanded graphite, stirring and soaking for 30min to obtain an aqueous solution A containing soluble aluminum salt, a dispersing agent and the expanded graphite;
the preparation method of the expanded graphite comprises the following steps:
weighing 1g of natural crystalline flake graphite and 0.4g of KMnO 4 Mixed acid (HNO) with 18mL 3 And H 3 PO 4 The volume ratio of (1: 2), adding the materials into a 500mL beaker, reacting for 40min at 40 ℃, separating, washing the separated solid matter to be neutral, drying for 4h at 60 ℃, and then placing the solid matter in a microwave oven to expand for 30s with the power of microwave expansion being 750W to obtain expanded graphite with the expansion volume of 300 mL/g;
(b) slowly adding 40mL of ammonia water into the aqueous solution A at the speed of 3g/min, continuously stirring for 30min after the dropwise addition is finished, carrying out ultrasonic treatment for 2h with the ultrasonic power of 600W, standing until the temperature is room temperature, washing, carrying out suction filtration, and activating for 3h at 170 ℃ to obtain the alumina modified expanded graphite adsorbent.
Example 2
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, which is the same as example 1 except that absolute ethanol in step (a) was replaced with methanol, and the remaining steps and process parameters were the same as those of example 1.
Example 3
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, which comprises the same steps and process parameters as in example 1, except that the anhydrous ethanol in step (a) is replaced by propylene glycol.
Example 4
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, which comprises the same steps and process parameters as in example 1, except that n-butanol was used instead of anhydrous ethanol in step (a).
Example 5
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, which comprises the same steps and process parameters as in example 1, except that the amount of anhydrous ethanol used in step (b) is 30 mL.
Example 6
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, which comprises the same steps and process parameters as in example 1, except that the amount of dehydrated ethanol used in step (b) is 40 mL.
Example 7
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, which comprises the same steps and process parameters as in example 1, except that the amount of anhydrous ethanol used in step (b) is 10 mL.
Example 8
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, except that in step (a), 0.1176g of Al (NO) was weighed based on the mass ratio of alumina to expanded graphite being 0.04:1 3 ) 3 ·9H 2 Dissolving O and 25mL of absolute ethyl alcohol in a 500mL beaker, adding 125mL of distilled water and 0.4g of expanded graphite, stirring and soaking for 30min to obtain an aqueous solution A containing soluble aluminum salt, a dispersing agent and the expanded graphite;
the preparation process and step (b) of the expanded graphite were the same as in example 1.
Example 9
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, except that in step (a), 0.2353g of Al (NO) was weighed out based on the mass ratio of alumina to expanded graphite being 0.08:1 3 ) 3 ·9H 2 Dissolving O and 25mL of absolute ethyl alcohol in a 500mL beaker, adding 125mL of distilled water and 0.4g of expanded graphite, stirring and soaking for 30min to obtain an aqueous solution A containing soluble aluminum salt, a dispersing agent and the expanded graphite;
the preparation process and step (b) of the expanded graphite were the same as in example 1.
Example 10
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, except that in step (a), 0.2941g of Al (NO) was weighed based on the mass ratio of alumina to expanded graphite being 0.10:1 3 ) 3 ·9H 2 Dissolving O and 25mL of absolute ethyl alcohol in a 500mL beaker, adding 125mL of distilled water and 0.4g of expanded graphite, stirring and soaking for 30min to obtain an aqueous solution A containing soluble aluminum salt, a dispersing agent and the expanded graphite;
the preparation process and step (b) of the expanded graphite were the same as in example 1.
Example 11
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, except that in step (a), 0.3529g of Al (NO) was weighed based on the mass ratio of alumina to expanded graphite being 0.12:1 3 ) 3 ·9H 2 Dissolving O and 25mL of absolute ethyl alcohol in a 500mL beaker, adding 125mL of distilled water and 0.4g of expanded graphite, stirring and soaking for 30min to obtain an aqueous solution A containing soluble aluminum salt, a dispersing agent and the expanded graphite;
the preparation process and step (b) of the expanded graphite were the same as in example 1.
Example 12
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, which comprises the same steps and process parameters as in example 1, except that the activation temperature in step (b) is 500 ℃ and the activation time is 3 hours.
Example 13
This example provides a method for preparing an alumina-modified expanded graphite adsorbent, in which in step (b), ammonia water is slowly added to the aqueous solution a instead of directly mixing the aqueous solution a with ammonia water, and the remaining steps and process parameters are the same as those in example 1.
Example 14
The embodiment provides a preparation method of an alumina modified expanded graphite adsorbent, which comprises the following steps:
(a) 0.3918g of Al is weighed according to the mass ratio of the alumina to the expanded graphite of 0.06:1 2 (SO 4 ) 3 ·18H 2 Dissolving O and 25mL of absolute ethyl alcohol in a 500mL beaker, adding 125mL of distilled water and 0.4g of expanded graphite, stirring and soaking for 30min to obtain an aqueous solution A containing soluble aluminum salt, a dispersing agent and the expanded graphite;
the preparation method of the expanded graphite comprises the following steps:
weighing 1g of natural crystalline flake graphite and 0.4g of KMnO 4 Mixed with 15mL of a mixed acid (HNO) 3 And H 3 PO 4 In a volume ratio of 1:2) were added together in a 500mL beaker and reacted at 40 ℃ for 40minThen, separating, washing the solid matter obtained by separation to be neutral, drying for 4h at 60 ℃, then placing the solid matter in a microwave oven to expand for 30s, wherein the power of microwave expansion is 650W, and obtaining expanded graphite, and the expansion volume of the expanded graphite is 280 mL/g;
(b) slowly adding 40mL of sodium hydroxide solution (the mass fraction of the sodium hydroxide is 30%) into the aqueous solution A at the speed of 3g/min, continuously stirring for 30min after the dropwise addition, carrying out ultrasonic treatment for 2h, carrying out ultrasonic treatment at the power of 800W, standing to room temperature, carrying out suction filtration, and activating for 8h at the temperature of 300 ℃ to obtain the alumina modified expanded graphite adsorbent.
Comparative example 1
This comparative example provides a method for preparing an alumina-modified expanded graphite adsorbent, which was the same as example 1 except that anhydrous ethanol was not added to the aqueous solution a of step (a), and the process parameters were the same.
Comparative example 2
The comparative example provides a preparation method of an alumina modified expanded graphite adsorbent, anhydrous ethanol in the aqueous solution A in the step (a) is replaced by polyvinyl alcohol and propylene glycol, the weight ratio of the polyvinyl alcohol to the propylene glycol is 1:1, and the rest steps and process parameters are the same as those in the example 1.
To verify the technical effects of the respective examples and comparative examples, the following experiments were conducted.
Experimental example 1
The alumina-modified expanded graphite adsorbents provided in examples 1 to 14 and comparative examples 1 to 2 were tested for adsorption performance, while the expanded graphite as the raw material in example 1 was used as a control experiment. The method for testing the adsorption performance comprises the following steps: 60mg of an alumina modified expanded graphite adsorbent sample is taken, 40mL of Congo red solution (200mg/L) is subjected to oscillation adsorption for 25min at room temperature, and then the decolorization rate and the adsorption quantity are measured, wherein specific results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the adsorption performance of the alumina modified expanded graphite adsorbent prepared by the preparation method provided by the invention is obviously superior to that of expanded graphite.
Compared with the comparative example 1, the adsorption performance of the alumina modified expanded graphite adsorbent prepared by the preparation method provided by the invention is obviously superior to that of the alumina modified expanded graphite adsorbent prepared without adding a dispersant; compared with the comparative example 2, the adsorption performance of the alumina modified expanded graphite adsorbent prepared by the preparation method provided by the invention is superior to that of the alumina modified expanded graphite adsorbent prepared by taking polyvinyl alcohol and propylene glycol as dispersing agents.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting 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.
Claims (22)
1. The preparation method of the alumina modified expanded graphite adsorbent is characterized by comprising the following steps:
providing an aqueous solution A containing a soluble aluminum salt, a dispersant and expanded graphite;
mixing the aqueous solution A and an alkaline substance to enable soluble aluminum salt to react with the alkaline substance to generate aluminum hydroxide, performing ultrasonic treatment, standing, separating at 15-25 ℃, and activating the solid substance obtained by separation to obtain an alumina modified expanded graphite adsorbent;
wherein the dispersant comprises alcohols with carbon atoms of C1-C4;
the mass ratio of the soluble aluminum salt, the dispersant and the expanded graphite in the aqueous solution A is (0.1-0.6) to (10-30) to (0.2-2).
2. The method of claim 1, wherein the dispersant comprises any one of methanol, ethanol, propanol, or butanol, or a combination of at least two thereof.
3. The production method according to claim 1, wherein the dispersant comprises ethanol.
4. The method of claim 1, wherein the alkaline substance comprises any one of ammonia, sodium hydroxide or potassium hydroxide or a combination of at least two of them.
5. The production method according to claim 1, wherein the basic substance includes ammonia water.
6. The method as claimed in claim 1, wherein the expanded volume of the expanded graphite in the aqueous solution A is 180-300 mL/g.
7. The method according to claim 1, wherein the mass ratio of the soluble aluminum salt, the dispersant and the expanded graphite in the aqueous solution A is (0.12-0.55): (12-28): (0.3-1.9).
8. The method according to claim 1, wherein the mass ratio of the basic substance to the soluble aluminum salt in the aqueous solution A is (20-40): (0.1-0.6).
9. The production method according to claim 1, wherein a basic substance is added dropwise to the aqueous solution A to effect the reaction, and the addition rate of the basic substance is 2 to 5 g/min.
10. The method as claimed in claim 1, wherein the power of the ultrasound is 480-900W, and the time of the ultrasound is 0.5-3 h.
11. The method according to claim 1, wherein the activation temperature is 80-500 ℃ and the activation time is 3-10 hours.
12. The method according to any one of claims 1 to 11, wherein the soluble aluminum salt in the aqueous solution a comprises any one of aluminum nitrate, aluminum chloride or aluminum sulfate or a combination of at least two thereof.
13. The production method according to any one of claims 1 to 11, wherein the expanded graphite comprises natural flake graphite.
14. The method according to any one of claims 1 to 11, wherein the method for producing expanded graphite comprises the steps of:
reacting the flake graphite, the intercalation agent and the oxidant, then separating, drying the graphite intermediate product obtained by separation, and performing microwave expansion to obtain the expanded graphite.
15. The preparation method of claim 14, wherein the mass ratio of the flake graphite to the intercalation agent to the oxidizing agent is 1 (10-25) to (0.1-0.6).
16. The method of claim 14, wherein the intercalant comprises nitric acid and phosphoric acid, and the volume ratio of nitric acid to phosphoric acid is 1: (0.5-3).
17. The method of claim 14, wherein the oxidizing agent comprises potassium permanganate.
18. The method according to claim 14, wherein the reaction temperature is 30 to 60 ℃ and the reaction time is 10 to 80 min.
19. The method as claimed in claim 14, wherein the power of the microwave expansion is 650-900W, and the time of the microwave expansion is 10-120 s.
20. The method of any one of claims 1 to 11, comprising the steps of:
(a) providing an aqueous solution A containing soluble aluminium salt, ethanol and expanded graphite; wherein the mass ratio of the soluble aluminum salt, the ethanol and the expanded graphite is (0.1-0.6) to (10-30) to (0.2-2), and the expansion volume of the expanded graphite is 180-300 mL/g;
(b) and (2) dropwise adding ammonia water into the aqueous solution A to enable the soluble aluminum salt and the ammonia water to react to generate aluminum hydroxide, carrying out ultrasonic treatment after dropwise adding is finished, standing, then carrying out separation at 15-25 ℃, and activating the intermediate product of the modified expanded graphite obtained by separation at 80-500 ℃ for 3-10h to obtain the alumina modified expanded graphite adsorbent.
21. An alumina-modified expanded graphite adsorbent, characterized by being produced by the method for producing an alumina-modified expanded graphite adsorbent according to any one of claims 1 to 20.
22. Use of the alumina-modified expanded graphite adsorbent of claim 21 in the field of water treatment.
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