CN116603505B - Modified composite ceramsite and preparation method and application thereof - Google Patents
Modified composite ceramsite and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 78
- 229960004624 perflexane Drugs 0.000 claims abstract description 38
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000013329 compounding Methods 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000010865 sewage Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- -1 iron-manganese-aluminum Chemical compound 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 238000000926 separation method Methods 0.000 claims 2
- 230000003213 activating effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 46
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 34
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 34
- 238000001179 sorption measurement Methods 0.000 description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- 239000005711 Benzoic acid Substances 0.000 description 17
- 235000010233 benzoic acid Nutrition 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 238000011068 loading method Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910018657 Mn—Al Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Water Treatment By Sorption (AREA)
Abstract
The invention provides a modified composite ceramsite, a preparation method and application thereof. The modified composite ceramsite comprises ceramsite, and graphene and perfluorohexane which are compounded on the ceramsite. The method comprises a compounding step and a modification step, wherein the compounding step comprises the following steps: putting the ceramsite into 0.1-10 mg/mL or 0.01-1 wt.% graphene solution for 0.5-5.0 hours to obtain composite ceramsite; the modification step comprises the following steps: and placing the composite ceramsite in a perfluorohexane solution with the volume fraction of more than 95% for more than 20 hours to obtain the modified composite ceramsite. The modified composite ceramsite has the ozone activating capability by modifying the composite ceramsite with perfluorohexane.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a modified composite ceramsite and a preparation method and application thereof.
Background
The carbon-based material comprises ceramsite, biochar and the like which are often used as adsorbents to adsorb macromolecules or pollutants in gas or solution, and has the advantages of low cost, simple preparation technology, environmental protection, no pollution, easy recycling and the like, and is widely applied to the fields of industry and scientific research. The inside of the haydite has a complex pore structure, and when water solution or gas enters the pore structure inside through the pores on the surface of the haydite, the water solution or gas is gradually adsorbed and screened by the surfaces of channels with different pore diameters. After the ceramic particles are adsorbed, the solution or gas can be purified to a certain extent. The surface property of micropores in the ceramsite determines the adsorption effect of the ceramsite on related pollutants in solution or gas, has obvious adsorption effect on some pollutants, and needs to strengthen the adsorption speed and adsorption quantity of some organic pollutants such as phenol, aniline and the like.
The conventional ceramsite surface treatment technology mainly comprises acid washing activation, but the ceramsite surface is easy to be polluted by acid after acid washing, and secondary pollution is caused in the purification process. And the pickling solution also causes pollution to peripheral equipment and environment in the discharging and recycling processes, and the pickling cost is obviously increased.
Disclosure of Invention
The present invention aims to solve the above technical problems existing in the prior art. The first aspect of the invention provides a modified composite ceramic particle, which comprises ceramic particles, graphene and perfluorohexane, wherein the graphene and the perfluorohexane are compounded on the ceramic particles.
The modified composite ceramsite provided by the invention enables the ceramsite loaded with graphene to quickly adsorb a large amount of aromatic ring-containing organic matters based on pi-pi interaction.
The perfluorohexane is used as a low-toxicity organic matter and has extremely strong solubility for oxygen, and the perfluorohexane is used for modifying the composite ceramsite, so that the graphene composite ceramsite has the ozone activating capability, and a large amount of hydroxyl free radicals generated by the activated ozone have a strong degradation effect on aromatic organic pollutants such as phenol, benzoic acid, antibiotics and the like adsorbed by the ceramsite.
Compared with the common ceramsite, the perfluorohexane modified graphene composite ceramsite disclosed by the invention not only can improve the adsorption efficiency on aromatic organic matters, but also can improve the activation effect on ozone and promote the degradation effect on the aromatic organic matters.
Preferably, in the modified composite ceramsite, the amount of graphene loaded on the ceramsite is 0.2-10 mg/g, and more preferably 5mg/g.
Preferably, in the modified composite ceramsite of the present invention, the amount of perfluorohexane carried on the ceramsite is 5.0 to 25.0mg/g, more preferably 15.0mg/g.
Another aspect of the present invention provides a method for preparing the modified composite ceramsite, comprising the steps of:
Compounding: putting the ceramsite into a graphene solution with the concentration of 0.1-10 mg/mL or 0.01-1.0 wt.% for 0.5-5.0 hours to obtain composite ceramsite;
Modification: the composite ceramsite is placed in a perfluorohexane solution with a volume fraction of 95% or more for 20 hours or more, preferably 20 to 30 hours, more preferably 20 to 24 hours, to obtain a modified composite ceramsite.
The preparation method of the invention has universality and can also be used for carbon-based materials such as composite biochar and the like. The method is simple and feasible, has high production efficiency, is environment-friendly and pollution-free, and has wide application prospect.
Preferably, in the compounding step, the ceramsite and the graphene solution are mixed in a mass ratio of 1:4-1:10, preferably in a mass ratio of 1:5.
Preferably, in the modification step, the composite ceramsite and the perfluorohexane solution are mixed in a mass ratio of 1:3-1:5, preferably in a mass ratio of 1:4.
Preferably, in the preparation method of the invention, the graphene solution is prepared by using the grapheme with the number of layers of 2-10 layers, preferably 2 layers, and the grapheme with the number of layers has larger specific surface area, so that the sewage treatment efficiency can be effectively improved during use.
Preferably, in the compounding step, the graphene solution of the ceramsite is separated, dried and heated, the heating is performed in a vacuum drying oven, the relative vacuum degree is-0.09 to-0.1 MPa, preferably-0.1 MPa, the heating temperature is 150-200 ℃, preferably 180 ℃, and the heating time is 0.5-2 hours, preferably 1 hour.
The heating temperature is too low or the heating time is too short, so that the degree of compounding of the ceramsite and the graphene is reduced, and the graphene loading is reduced; the heating temperature is too high or the heating time is too long, and the adsorption performance of the composite ceramsite is not obviously improved.
Preferably, the concentration of the graphene solution is 1.0-10 mg/mL.
The soaking time of the ceramsite in the graphene solution can be adjusted according to the concentration of the adopted graphene solution, and the higher the concentration of the graphene solution is, the shorter the soaking time is adopted.
Preferably, the ceramic particles are ferro-manganese-aluminum-based ceramic particles with the particle size of 2-5 mm and the porosity of 60-95%, preferably 70-90%, more preferably 75-85%.
The Fe-Mn-Al-based ceramsite has high porosity and stable structure, and is suitable for sewage treatment.
Preferably, the solvent of the graphene solution is NMP (N-methylpyrrolidone). Because the dispersibility of graphene in NMP is good. Specifically, the graphene solution of the present invention may be prepared as follows: and accurately weighing a proper amount of graphene, weighing a proper amount of NMP, and placing the graphene in the NMP for stirring and ultrasonic treatment. Wherein the stirring frequency is 200-1000 rpm, the stirring time is 0.5-2 hours, the ultrasonic power is 50-200W, and the ultrasonic time is more than 30 minutes to uniformly disperse the graphene.
Preferably, in both the compounding and modification steps, the drying is carried out in a vacuum oven at a drying temperature of ambient temperature (25 ℃.+ -. 5 ℃).
The composite ceramsite loaded with the perfluorohexane needs to be dried at normal temperature, and the phase change loss of the perfluorohexane ozone activator can be caused by the too high drying temperature (for example, more than 60 ℃).
In other embodiments of the present invention, the drying may be performed in other drying apparatuses as long as the composite ceramsite or the modified composite ceramsite can be dried.
Preferably, in the modification step, the composite ceramic particles are placed in a perfluorohexane solution having a volume fraction of 95% or more for 20 to 24 hours. The concentration of the perfluorohexane solution used cannot be too low, otherwise, the effect of sufficient modification cannot be achieved. In other embodiments of the invention, the time of modification (immersing the composite ceramsite in the perfluorohexane solution) may be adjusted according to the specific conditions of the wastewater treatment.
A third aspect of the present invention provides the use of the modified composite ceramsite described above in the treatment of wastewater, comprising placing the modified composite ceramsite at the inlet of ozone into the wastewater.
Preferably, the COD concentration of the sewage is 100-1000 mg/L, the gas flow rate of ozone entering the sewage is 30-50L/min, the volume ratio of the modified composite ceramsite to the sewage is 1:2-1:5, more preferably, the COD concentration of the sewage is 600mg/L, the flow rate of ozone entering the sewage is 50L/min, the volume ratio of the modified composite ceramsite to the sewage is 1:3, and the optimal adsorption and degradation effects on aromatic ring organic matters can be obtained.
Drawings
FIG. 1 is a graph showing the change in the concentration of phenol in a solution of the modified composite ceramsite of example 3 and ceramsites of comparative examples 1 to 3, respectively, with the reaction time, in a phenol solution of 5.0 g/L;
FIG. 2 is a graph showing the equilibrium adsorption rate of phenol in a solution of the modified composite ceramsite of example 3 and the ceramsite of comparative examples 1 to 3;
FIG. 3 shows the concentration of aniline in the solution after adding the modified composite ceramsite of example 3 and the ceramsite of comparative examples 1-3, respectively, to an aniline solution having a concentration of 5.0g/L as a function of reaction time;
FIG. 4 is a graph showing the equilibrium adsorption rate of aniline in the solution of the modified composite ceramsite of example 3 and the ceramsite of comparative examples 1 to 3;
FIG. 5 shows the concentration of benzoic acid in the solutions after the addition of the modified composite ceramsite of example 3 and the ceramsite of comparative examples 1-3, respectively, to a benzoic acid solution having a concentration of 1.5g/L as a function of reaction time;
FIG. 6 is a graph showing the equilibrium adsorption rate of benzoic acid in solution of the modified composite ceramsite of example 3 and the ceramsite of comparative examples 1-3;
FIG. 7 is a photograph of untreated Fe-Mn-Al based ceramsite;
Fig. 8 is a photograph of the iron-manganese-aluminum-based ceramsite after the graphene is compounded.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to examples. It should be understood that the following examples are only illustrative of specific embodiments of the present invention and are not intended to limit the scope of the present invention in any way.
The following raw materials and equipment used in the preparation examples, examples and comparative examples are as follows:
1. iron-manganese-aluminum-based ceramsite: the particle size was 5mm and purchased from Jin Rui ceramsite plant.
2. Perfluorohexane solution (CAS: 355-42-0): purity was 98% and purchased from an exploration website.
3. Ultraviolet spectrophotometer: specification LABII D60, available from Shanghai Meinada instruments Inc.
The perfluorohexane loading was determined as follows:
the mass of the composite ceramsite before and after modification and the load of perfluorohexane = (mass of modified composite ceramsite-mass of composite ceramsite)/mass of composite ceramsite were measured respectively using a weighing balance.
The graphene loading is determined as follows:
And respectively measuring the concentration changes of the graphene solutions before and after the compounding by using an ultraviolet spectrophotometer, wherein the graphene solution before the compounding is the graphene solution without adding the ceramsite, the graphene solution after the compounding is the graphene solution after filtering out the compound ceramsite, and obtaining the loading amount of the graphene on the ceramsite according to the concentration difference of the solution. Specifically, the absorbance of the graphene solution before and after the compounding at the wavelength of 274nm is measured by an ultraviolet spectrophotometer, and the concentration of the graphene solution before and after the compounding can be obtained according to lambert beer law a/l=α·c G (wherein a is the absorbance at 274nm, C G is the graphene concentration, α is the absorption coefficient, and l is the optical path length). According to the concentration difference of the graphene solution before and after the compounding, the volume of the graphene solution and the mass of the ceramsite, the loading capacity of the graphene on the ceramsite can be obtained.
Embodiments of the present invention will be described in detail with reference to examples and comparative examples.
Example 1
The modified composite ceramsite is prepared according to the following steps:
(1) Preparing graphene solution: weighing 0.2g of graphene solid (a sample is black flaky), adding the graphene solid into 100mL of NMP, stirring for 1 hour at 500rpm by using a magnetic stirrer, and then placing the mixture into an ultrasonic cleaner for 0.5 hour by using 100W power ultrasonic to obtain a completely dispersed graphene solution, wherein the solution is transparent and light black;
(2) Compounding: and (3) cleaning 20g of the iron-manganese-aluminum-based ceramsite by using deionized water, then placing the cleaned iron-manganese-aluminum-based ceramsite into a 60 ℃ oven for drying, wherein the iron-manganese-based ceramsite is yellow brown (refer to fig. 7), the surface of the iron-manganese-aluminum-based ceramsite is rough, then adding the iron-manganese-based ceramsite into the graphene solution prepared in the step (1), and stirring the graphene solution to make the iron-manganese-based ceramsite fully contact with the graphene solution. After 1 hour of standing at room temperature, the color of the graphene solution gradually became transparent, and filtration was performed using filter paper. And (3) drying the obtained ceramsite in a vacuum drying oven at 25 ℃ for 2 hours, wherein the graphene solution compounded on the surface of the ceramsite is completely dried, and the surface of the ceramsite is light black. And taking out the dried composite ceramsite, and putting the composite ceramsite into a vacuum drying oven at 180 ℃ for reduction and compounding for 1 hour. The surface of the composite ceramsite is light black after being taken out (refer to figure 8).
(3) Modification: and putting the composite ceramsite into 50mL of 98% perfluorohexane solution, and slowly stirring for 20 hours at room temperature to enable the solution to fully contact with the graphene composite ceramsite. Separating the perfluorohexane modified composite ceramsite from the solution by using filter paper, and putting the obtained perfluorohexane modified composite ceramsite into a vacuum drying oven at 25 ℃ for drying for 2 hours to obtain the modified composite ceramsite.
The loading amounts of the graphene and the perfluorohexane on the modified composite ceramsite are 1.0mg/g and 15mg/g respectively.
Example 2
The modified composite ceramsite is prepared according to the following steps:
(1) Preparing graphene solution: weighing 0.5g of graphene solid, adding the graphene solid into 100mL of NMP, stirring for 1 hour at 500rpm by using a magnetic stirrer, and then placing the mixture into an ultrasonic cleaner to carry out ultrasonic treatment for 1 hour by using 100W power to obtain a completely dispersed graphene solution, wherein the solution is semitransparent black;
(2) Compounding: and (3) cleaning 20g of iron-manganese-aluminum-based ceramsite by using deionized water, then placing the cleaned iron-manganese-aluminum-based ceramsite into a 60 ℃ oven for drying, wherein the iron-manganese-aluminum-based ceramsite is yellow brown and has a rough surface, then adding the iron-manganese-aluminum-based ceramsite into the graphene solution prepared in the step (1), and stirring to enable the iron-manganese-aluminum-based ceramsite to be fully contacted with the graphene solution. After 1 hour of standing at room temperature, the graphene solution was gradually lightened in color, and filtration was performed using filter paper. The obtained ceramsite is put into a vacuum drying oven at 25 ℃ to be dried for 2 hours. At the moment, the graphene solution compounded on the surface of the ceramsite is completely dried, and the surface of the ceramsite is light black. And taking out the dried composite ceramsite, and putting the composite ceramsite into a vacuum drying oven at 180 ℃ for reduction and compounding for 1 hour. The surface of the composite ceramsite is smooth and light black after being taken out.
(3) Modification: and putting the composite ceramsite into 50mL of 98% perfluorohexane solution, and slowly stirring at room temperature for 24 hours to enable the solution to fully contact with the graphene composite ceramsite. Separating the perfluorohexane modified composite ceramsite from the solution by using filter paper, and putting the obtained perfluorohexane modified composite ceramsite into a vacuum drying oven at 25 ℃ for drying for 2 hours to obtain the modified composite ceramsite.
The loading amounts of the graphene and the perfluorohexane on the modified composite ceramsite are 2.5mg/g and 15mg/g respectively.
Example 3
The modified composite ceramsite is prepared according to the following steps:
(1) Preparing graphene solution: 1.0g of graphene solid (a sample is black flaky) is weighed and added into 100mL of NMP, the mixture is stirred for 1 hour at 500rpm by using a magnetic stirrer, and then the mixture is placed into an ultrasonic cleaner and subjected to ultrasonic treatment with 100W power for 1 hour, so that a completely dispersed graphene solution is obtained, and the solution is opaque black;
(2) Compounding: and (3) cleaning 20g of the iron-manganese-aluminum-based ceramsite by using deionized water, drying in a 60 ℃ oven, wherein the iron-manganese-aluminum-based ceramsite is yellow brown and has a rough surface, adding the iron-manganese-based ceramsite into the graphene solution prepared in the step (1), and stirring to make the iron-manganese-based ceramsite fully contact with the graphene solution. After 1 hour of standing at room temperature, the color of the graphene solution was significantly lightened, and filtration was performed using filter paper. And (3) drying the obtained ceramsite in a vacuum drying oven at 25 ℃ for 2 hours, wherein the graphene solution compounded on the surface of the ceramsite is completely dried, and the surface of the ceramsite is black. And taking out the dried composite ceramsite, and putting the composite ceramsite into a vacuum drying oven at 180 ℃ for reduction and compounding for 1 hour. The surface of the composite ceramsite is smooth and bright black after being taken out.
(3) Modification: and putting the composite ceramsite into 50mL of 98% perfluorohexane solution, and slowly stirring at room temperature for 24 hours to enable the solution to fully contact with the graphene composite ceramsite. Separating the perfluorohexane modified composite ceramsite from the solution by using filter paper, and putting the obtained perfluorohexane modified composite ceramsite into a vacuum drying oven at 25 ℃ for drying for 2 hours to obtain the modified composite ceramsite.
The loading amounts of the graphene and the perfluorohexane on the modified composite ceramsite are 5.0mg/g and 15mg/g respectively.
Comparative example 1
The Fe-Mn-Al-based ceramic particles are not compounded and modified, and the morphology of the untreated Fe-Mn-Al-based ceramic particles is shown in figure 7.
Comparative example 2
Similar to the preparation of example 3, the difference is that only the iron-manganese-aluminum-based ceramsite is compounded, the step of modifying the composite ceramsite is not included, and the appearance of the unmodified composite ceramsite is shown in fig. 8.
Comparative example 3
Only the ferromanganese aluminum-based ceramsite is modified, and the graphene compounding step is not carried out, and the specific preparation method is as follows:
20g of iron-manganese-aluminum-based ceramsite is cleaned by deionized water, then is dried in a baking oven at 60 ℃, is put into 50mL of 98% perfluorinated hexane solution, and is slowly stirred for 24 hours at room temperature to enable the solution to be fully contacted with the ceramsite. Separating the perfluor hexane modified ceramsite from the solution by using filter paper, and putting the obtained perfluor hexane modified ceramsite into a vacuum drying oven at 25 ℃ for drying for 2 hours to obtain the modified ceramsite.
The loading of the perfluorohexane on the modified ceramsite is 15mg/g.
And respectively characterizing the adsorption rate of the obtained various ceramsite to the aromatic organic matters. The haydites of example 1 and comparative examples 1-3 were used to adsorb phenol, aniline, and benzoic acid at different concentrations, respectively.
Taking the adsorption of phenol in the solution by the modified composite ceramsite of example 3 as an example: 5g of the modified composite ceramsite of example 3 is placed into a phenol solution with the volume of 100mL and the concentration of 5.0g/L, the solution is continuously stirred by a magnetic stirrer at 200-600 rpm, the solution is stood for a period of time to obtain a supernatant, and the supernatant is placed into an ultraviolet spectrophotometer to measure the absorbance of the phenol solution at 270nm, so as to obtain the concentration change of phenol in the solution.
The same process conditions were used for the adsorption of the corresponding aromatic organic compounds (aniline absorption wavelength of 256nm or benzoic acid absorption wavelength of 250 nm) by the other examples and comparative examples, unless otherwise specified.
FIG. 1 shows the reaction time dependence of the phenol concentration in the solution after adding 5.0g of the ceramsite of example 3 and comparative examples 1-3 to a phenol solution having a concentration of 5.0g/L, respectively.
As shown in FIG. 1, after the modified composite ceramsite of example 3 is added into the phenol solution, the phenol concentration in the solution is rapidly reduced along with the time increase, the adsorption speed is gradually reduced after 6 hours (h), and the phenol concentration change in the solution gradually becomes stable after 48 hours.
FIG. 2 is a graph showing the equilibrium adsorption rates of the modified composite ceramsite of example 3 and the ceramsite of comparative examples 1 to 3. As shown in fig. 2, compared with the common ceramsite of comparative example 1, the adsorption rate of the modified composite ceramsite of example 3 in 5g/L phenol solution can be improved by 55%; compared with the composite ceramsite of comparative example 2, the adsorption rate of the modified composite ceramsite of example 3 in 5g/L of phenol solution can be improved by 28%; compared with the modified ceramsite of comparative example 3, the adsorption rate of the modified composite ceramsite of example 3 in a phenol solution of 5g/L can be improved by 16%.
FIG. 3 shows the concentration of aniline in the solution as a function of reaction time after adding 5g of the ceramsite of example 3 and comparative examples 1-3, respectively, to an aniline solution having a concentration of 5.0 g/L. As shown in FIG. 3, after the modified composite ceramsite of example 3 is added into the aniline solution, the concentration of aniline in the solution is rapidly reduced along with the increase of time, the adsorption speed is gradually reduced after 6 hours, and the concentration change of aniline in the solution gradually becomes stable after 48 hours.
FIG. 4 shows the equilibrium adsorption rates of the modified composite ceramsite of example 3 and the ceramsite of comparative examples 1-3. As shown in fig. 4, compared with the common ceramsite of comparative example 1, the adsorption rate of the modified composite ceramsite of example 3 in 5g/L aniline solution can be improved by 29%; compared with the composite ceramsite of comparative example 2, the adsorption rate of the modified composite ceramsite of example 3 in 5g/L of aniline solution can be improved by 19%; compared with the modified ceramsite of comparative example 3, the adsorption rate of the modified composite ceramsite of example 3 in 5g/L aniline solution can be improved by 10%.
FIG. 5 shows the concentration of benzoic acid in the solutions after the addition of 20g of the ceramsite of example 3 and comparative examples 1-3, respectively, to a benzoic acid solution having a concentration of 1.5g/L as a function of the reaction time. As shown in FIG. 5, after the perfluoro hexane modified graphene composite ceramsite is added into the benzoic acid solution, the benzoic acid content in the solution is rapidly reduced along with the time increase, the adsorption speed is gradually reduced after 6 hours, and the benzoic acid concentration change in the solution gradually becomes stable after 48 hours.
FIG. 6 is a graph showing the equilibrium adsorption rates of the modified composite ceramsite of example 3 and the ceramsite of comparative examples 1 to 3. As shown in fig. 6, compared with the common ceramsite of comparative example 1, the adsorption rate of the modified composite ceramsite of example 3 in 1.5g/L benzoic acid solution can be improved by 42%; compared with the composite ceramsite of comparative example 2, the adsorption rate of the modified composite ceramsite of example 3 in 1.5g/L benzoic acid solution can be improved by 35%; compared with the modified ceramsite of comparative example 3, the adsorption rate of the modified composite ceramsite of example 3 in 1.5g/L benzoic acid solution can be improved by 18%.
Ozone degradation test:
taking the degradation of phenol in sewage by the modified composite ceramsite in example 3 as an example, the initial COD of phenol in sewage is 2470mg/L:
The modified composite ceramsite of the embodiment 3 and the comparative examples 1-3 are respectively placed at the inlet of an ozone aeration head, the gas flow rate of ozone entering a sewage sample is controlled to be 50L/min, an ultraviolet spectrophotometer is adopted to measure COD values (unit is mg/L) of the modified composite ceramsite when the modified composite ceramsite respectively reacts in the sewage sample for 30, 60, 90 and 120min, and the degradation rate is calculated in the following way:
degradation rate P= [ C 0-C]/C0 ×100%
C: COD value of pollutant after catalytic degradation for corresponding time
C 0: COD value of the initial contaminant
The corresponding COD values are shown in Table 1.
TABLE 1
| Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| 0min | 2470 | 2470 | 2470 | 2470 |
| 30min | 1630 | 2013 | 1945 | 1899 |
| 60min | 1060 | 1656 | 1598 | 1387 |
| 90min | 565 | 1125 | 1034 | 903 |
| 120min | 84 | 678 | 530 | 426 |
Similarly, example 3 and comparative examples 1 to 3 were tested for the degradation effect of aniline in sewage. The initial COD of aniline in the sewage is 2610mg/L, and after adsorption degradation is carried out by using different ceramsites, the corresponding COD values are shown in Table 2.
TABLE 2
| Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| 0min | 2610 | 2610 | 2610 | 2610 |
| 30min | 1695 | 2078 | 2002 | 1953 |
| 60min | 1043 | 1703 | 1615 | 1423 |
| 90min | 505 | 1175 | 1058 | 941 |
| 120min | 71 | 706 | 640 | 468 |
Example 3 and comparative examples 1 to 3 were tested for the degradation effect of benzoic acid in sewage. The initial COD of benzoic acid in the sewage is 2520mg/L, and after adsorption degradation is carried out by using different ceramsites respectively, the corresponding COD values are shown in Table 3.
TABLE 3 Table 3
It can be seen that the degradation rate of phenol of the modified composite ceramsite provided in the embodiment 3 of the invention is improved by about 33% compared with that of the common ceramsite in the comparative example 1 after 120min under the same reaction conditions, is improved by about 23% compared with that of the composite ceramsite in the comparative example 2, and is improved by about 17% compared with that of the modified ceramsite in the comparative example 3; the degradation rate of the aniline is improved by about 33% compared with the common ceramsite of the comparative example 1, is improved by about 29% compared with the composite ceramsite of the comparative example 2, and is improved by about 19% compared with the modified ceramsite of the comparative example 3; the degradation rate of the benzoic acid is improved by about 38 percent compared with the common ceramsite of the comparative example 1, is improved by about 32 percent compared with the composite ceramsite of the comparative example 2, and is improved by about 20 percent compared with the modified ceramsite of the comparative example 3. According to the modified composite ceramsite disclosed by the invention, the loading capacity of perfluorohexane is improved through loading graphene, and the degradation effect on aromatic organic matters is obviously improved when ozone is used for degrading organic matters in sewage.
While the invention has been described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a further detailed description of the invention in connection with specific embodiments, and it is not intended to limit the invention to the specific embodiments described. Various changes in form and detail may be made therein by those skilled in the art, including a few simple inferences or alternatives, without departing from the spirit and scope of the present invention.
Claims (8)
1. The modified composite ceramsite is characterized by being an iron-manganese-aluminum-based ceramsite, and comprises ceramsite, graphene and perfluorohexane which are compounded on the ceramsite;
the modified composite ceramsite is prepared by the following method, which comprises the following steps:
compounding: placing the ceramsite into 0.1-10 mg/mL or 0.01-1.0 wt% graphene solution for 0.5-5.0 hours to obtain composite ceramsite, wherein in the compounding step, solid-liquid separation, drying and heating are carried out on the graphene solution of the ceramsite, and the heating temperature is 150-200 ℃ for 0.5-2.0 hours;
modification: and placing the composite ceramsite in a perfluorohexane solution with the volume fraction of more than 95% for more than 20 hours to obtain the modified composite ceramsite.
2. The modified composite ceramsite according to claim 1, wherein the amount of graphene loaded on the ceramsite is 0.2-10.0 mg/g.
3. The modified composite ceramic aggregate according to claim 1 or 2, wherein the amount of perfluorohexane carried on the ceramic aggregate is 5.0 to 25.0 mg/g.
4. The modified composite ceramsite of claim 1 or 2, wherein in the compounding step, the ceramsite and the graphene solution are mixed in a mass ratio of 1:4 to 1:10.
5. The modified composite ceramic aggregate according to claim 1 or 2, wherein in the modification step, the composite ceramic aggregate and the perfluorohexane solution are mixed at a mass ratio of 1:3 to 1:5.
6. The modified composite ceramsite according to claim 1 or 2, wherein the preparation method further satisfies one or more of the following:
preparing a graphene solution by using graphene with 2-10 layers;
The particle size of the ceramsite is 2-5 mm, and the porosity is 60% -95%;
The solvent of the graphene solution is N-methyl pyrrolidone;
the concentration of the graphene solution is 1.0-10 mg/mL;
In the compounding step, drying is carried out in a vacuum drying oven, and the drying temperature is normal temperature;
In the modification step, solid-liquid separation and drying are carried out on the perfluorohexane solution of the composite ceramsite, the drying is carried out in a vacuum drying oven, and the drying temperature is normal temperature.
7. The use of the modified composite ceramic particles according to any one of claims 1 to 6 in sewage treatment, wherein the modified composite ceramic particles are placed at an inlet of ozone into sewage.
8. The application of claim 7, wherein the COD concentration of the sewage is 100-1000 mg/L, the gas flow rate of ozone entering the sewage is 30-50L/min, and the volume ratio of the modified composite ceramsite to the sewage is 1:2-1:5.
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