CN115228437B - Surface modification method for making active carbon surface positive - Google Patents
Surface modification method for making active carbon surface positive Download PDFInfo
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- CN115228437B CN115228437B CN202210992876.3A CN202210992876A CN115228437B CN 115228437 B CN115228437 B CN 115228437B CN 202210992876 A CN202210992876 A CN 202210992876A CN 115228437 B CN115228437 B CN 115228437B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 238000002715 modification method Methods 0.000 title claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 49
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 235000011837 pasties Nutrition 0.000 claims 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 abstract description 22
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000005611 electricity Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- -1 perfluoro octoate anions Chemical class 0.000 description 8
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000861 blow drying Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- VORLTHPZWVELIX-UHFFFAOYSA-N 1-methyl-2h-quinoline Chemical group C1=CC=C2N(C)CC=CC2=C1 VORLTHPZWVELIX-UHFFFAOYSA-N 0.000 description 2
- MMKYUTRZRJHJRT-UHFFFAOYSA-N CN1C2=CC=CC=C2C=CC1.Cl Chemical group CN1C2=CC=CC=C2C=CC1.Cl MMKYUTRZRJHJRT-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000003238 esophagus Anatomy 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
Abstract
The invention discloses a surface modification method for making active carbon positive in aqueous solution, which synthesizes chloridized-1-methylquinoline on the surface of the active carbon pretreated by hydrochloric acid in situ. The invention utilizes the alkalinity of quinoline to enable the quinoline to be adsorbed on an acidic adsorption site on the activated carbon treated by hydrochloric acid, then reacts with methanol on the surface of the activated carbon under the catalysis of concentrated hydrochloric acid to synthesize the chloridized-1-methylquinoline in situ, so that the activated carbon has positive electricity on the surface of an aqueous solution, thereby improving the adsorption rate and adsorption capacity of the activated carbon on perfluorooctanoic acid.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a surface modification method for making the surface of active carbon positive.
Background
Perfluorooctanoic acid (PFOA) has unique thermal stability, chemical stability and high surface activity, and is widely used in the production of many daily and industrial products. The C-F bond of PFOA has extremely high bond energy, so that PFOA molecules are difficult to be photolyzed, hydrolyzed and biodegraded. Studies have shown that PFOA can enter the human body through the respiratory tract, esophagus, etc., causing serious damage to the reproductive system, liver and kidneys of people, and possibly even causing cancer. Therefore, the search for a rapid, efficient and low-cost PFOA removal method has important significance for ecological environment protection and human health.
Activated carbon is the most common carbon adsorbent material. PFOA molecules are large in size, have certain hydrophobic characteristics and exist in the form of perfluoro octoate anions in the solution. Therefore, removal of PFOA in aqueous solutions using both hydrophobic and electrostatic adsorption of adsorbents is the most efficient method. However, the surface of the common activated carbon contains a large amount of oxygen-containing functional groups, the functional groups enable the surface of the activated carbon to be electronegative in an aqueous solution, and perfluoro octoate ions are electronegative in the aqueous solution, so that the surface of the activated carbon is extremely easy to repel, and the adsorption performance of the activated carbon on perfluoro octoate ions is reduced. In the prior art, other compounds which make the active carbon positive are grafted or loaded on the surface of the active carbon, such as metal cations or 3-chloro-2-hydroxypropyl trimethylammonium chloride and the like, so as to achieve the aim of improving the adsorption effect, but the loaded metal ions are easy to fall off from the surface of the active carbon to cause secondary pollution, and the long carbon chain of the epoxy grafted quaternary ammonium salt can increase the steric hindrance (overlapping atomic electron clouds and representing repulsive force) of PFOA adsorption, so that the improvement of the PFOA adsorption performance is influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a modification method for making active carbon positive in the surface of an aqueous solution, so as to solve the problems that the active carbon in the prior art has poor effect of absorbing perfluorooctanoic acid in water and compounds loaded on the surface of the active carbon are easy to fall off.
In order to solve the technical problems, the invention adopts the following technical scheme:
a surface modification method for making the surface of active carbon positive specifically comprises the following steps:
step 1: screening the activated carbon, cleaning the activated carbon by deionized water, and heating and drying the activated carbon for later use;
step 2: adding the activated carbon obtained in the step 1 into hydrochloric acid with the concentration of 1mol/L for soaking, and then drying to constant weight after washing;
step 3: adding quinoline into the activated carbon obtained in the step 2; the ratio of the activated carbon to the quinoline is 1g: (0.5-3.5) mL, and slightly stirring for 0.5-1 h to enable the activated carbon to fully adsorb quinoline;
step 4: slowly adding concentrated hydrochloric acid into the mixture in the step 3, wherein the mole number of the added concentrated hydrochloric acid is 3-5 times that of quinoline, and slightly stirring for 0.5-1 h after the concentrated hydrochloric acid is added dropwise, so that the activated carbon fully adsorbs the concentrated hydrochloric acid;
step 5: distilling the mixture obtained in the step 4 under reduced pressure at 45 ℃;
step 6: transferring the product obtained in the step 5 into a hydrothermal reaction kettle, adding methanol, uniformly mixing, sealing, and reacting at 145-180 ℃ for 6-12h; wherein, the mole number of methanol is 2-3 times of that of quinoline;
step 7: after the reaction kettle is cooled, taking out the product in the reaction kettle, and distilling under reduced pressure at 70 ℃ to remove unreacted methanol;
step 8: repeatedly washing the activated carbon treated in the step 7 with absolute ethyl alcohol, repeatedly washing with deionized water, and drying to obtain the activated carbon modified by the chloridized-1-methylquinoline.
In the prior art, in order to improve the performance of activated carbon in adsorbing PFOA, the surface of the activated carbon is often directly loaded with metal ions or grafted with compounds such as 3-chloro-2-hydroxypropyl trimethylammonium chloride. However, metal ions are easy to fall off, and the long-chain structure of 3-chloro-2-hydroxypropyl trimethylammonium chloride can increase the steric hindrance of pollutant adsorption and block micropores of the activated carbon, so that the adsorption performance of the activated carbon is improved. According to the invention, the quaternary ammonium salt with a non-long-chain structure, namely the chloridized-1-methylquinoline, is synthesized on the surface of the activated carbon in situ, so that the adsorption quantity of the activated carbon to the perfluorooctanoate ions can be increased, and the adsorption speed of the activated carbon to the perfluorooctanoate ions can be increased, and the adsorption effect of the activated carbon to the perfluorooctanoate ions can be improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the method comprises the steps of firstly pretreating the activated carbon by acid, firstly washing inorganic salt and ash left in the preparation process of the activated carbon, generating new pores and increasing the specific surface area of the activated carbon; secondly, the acidic oxygen-containing functional group of the activated carbon is increased, and the alkalinity of the quinoline is utilized, so that the quinoline can be adsorbed on the surface of the activated carbon, is not easy to fall off from the surface of the activated carbon, and can improve the adsorption effect of the activated carbon on the perfluorooctanoic acid.
2. In the method, concentrated hydrochloric acid instead of HCl gas is used as a catalyst, and water is removed through reduced pressure distillation, so that the problems of environmental pollution caused by HCl gas and inconvenience in transportation and storage are avoided.
Drawings
Fig. 1 is an SEM image of unmodified activated carbon.
FIG. 2 is a graph of the activated carbon modified with 1-methylquinoline chloride obtained in example 2.
Fig. 3 is a graph of PFOA performance evaluation of activated carbon adsorption.
Detailed Description
The invention will be further described with reference to the drawings and examples.
1. Example
Example 1
(1) Sieving activated carbon with standard sieve to obtain 20-60 mesh activated carbon, cleaning with deionized water for 3-6 times to remove impurities and dust on the surface of activated carbon, drying in a blow drying oven at 110deg.C to constant weight, cooling to room temperature, and packaging into sample bag;
(2) Placing the 5g active carbon obtained in the step (1) in a beaker, adding 400 mL of hydrochloric acid with the concentration of 1mol/L, and soaking 24h at room temperature. Washing with deionized water, suction filtering for 3-6 times, and drying to constant weight;
(3) 2.5g of the activated carbon obtained in the step (2) is weighed and added into a three-necked flask, the three-necked flask is placed into an ice-water bath, and the temperature in the three-necked flask is controlled to be not more than 50 ℃; then quinoline of 2 mL was added dropwise.
(4) After the activated carbon adsorbs quinoline 0.5 and h, slowly adding 4.2 mL of concentrated hydrochloric acid into the three-necked flask through a dropping funnel;
(5) After the concentrated hydrochloric acid is added dropwise to the mixture of 0.5 and h, the mixture is placed in a three-neck flask in a constant-temperature water bath kettle at 45 ℃ for reduced pressure distillation;
(6) After the reduced pressure distillation is finished, all the active carbon and the solution in the three-neck flask are transferred to a hydrothermal synthesis reaction kettle, 1.37 and mL of methanol are respectively added, the mixture is sealed after being slightly and uniformly stirred by a glass rod, and the mixture is placed in an oven at 145 ℃ for reaction 6 h;
(7) Taking out the reaction kettle, naturally cooling to room temperature, transferring the activated carbon and the liquid into a three-necked flask, and distilling under reduced pressure at 70 ℃ to remove unreacted methanol;
(8) And (3) carrying out suction filtration and washing on the activated carbon for 3-6 times by using absolute ethyl alcohol, carrying out suction filtration and washing by using deionized water for 3-6 times, and then drying the obtained activated carbon in a drying oven at 70 ℃ until the weight is constant, thus obtaining the activated carbon modified by the chloridized-1-methylquinoline.
Wherein, the structural formula of the chloridized-1-methylquinoline is as follows:
example 2
(1) Sieving activated carbon with standard sieve to obtain 20-60 mesh activated carbon, cleaning with deionized water for 3-6 times to remove impurities and dust on the surface of activated carbon, drying in a blow drying oven at 110deg.C to constant weight, cooling to room temperature, and packaging into sample bag;
(2) Placing the 5g active carbon obtained in the step (1) in a beaker, adding 400 mL of hydrochloric acid with the concentration of 1mol/L, and soaking 24h at room temperature. Washing with deionized water, suction filtering for 3-6 times, and drying to constant weight;
(3) Weighing the activated carbon 2.5 and g obtained in the step (2), adding the activated carbon into a three-necked flask, placing the three-necked flask into an ice-water bath, and controlling the temperature in the three-necked flask to be not more than 50 ℃ through the ice-water bath; then quinoline 6.5. 6.5 mL was added dropwise.
(4) After the activated carbon adsorbs quinoline 0.5 and h, slowly adding 13.65 mL of concentrated hydrochloric acid into the three-necked flask through a dropping funnel;
(5) After the concentrated hydrochloric acid is added dropwise to the mixture of 0.5 and h, the mixture is placed in a three-neck flask in a constant-temperature water bath kettle at 45 ℃ for reduced pressure distillation;
(6) After the reduced pressure distillation is finished, all the activated carbon and the solution in the three-neck flask are transferred to a hydrothermal synthesis reaction kettle, 4.45mL of methanol is respectively added, the mixture is sealed after being slightly and uniformly stirred by a glass rod, and the mixture is placed in an oven at 145 ℃ for reaction 6 h;
(7) Taking out the reaction kettle, naturally cooling to room temperature, transferring the activated carbon and the liquid into a three-necked flask, and distilling under reduced pressure at 70 ℃ to remove unreacted methanol;
(8) Washing and suction-filtering the activated carbon with absolute ethyl alcohol for 3-6 times, washing and suction-filtering with deionized water for 3-6 times, and then drying the obtained activated carbon in a 70 ℃ oven until the weight is constant to obtain the activated carbon modified by the chloridized-1-methylquinoline.
Control example: 3-chloro-2-hydroxypropyl trimethylammonium chloride modified activated carbon
(1) Sieving activated carbon with standard sieve to obtain 20-60 mesh activated carbon, cleaning with deionized water for 3-6 times to remove impurities and dust on the surface of activated carbon, drying in a blow drying oven at 110deg.C to constant weight, cooling to room temperature, and packaging into sample bag;
(2) Placing the 5g active carbon obtained in the step (1) in a beaker, adding 400 mL of hydrochloric acid with the concentration of 1mol/L, and soaking 24h at room temperature. Washing with deionized water, suction filtering for 3-6 times, and drying to constant weight;
(3) 2.0 g active carbon obtained in the step (2) is placed in a 250 mL conical flask. 20 mL of 3-chloro-2-hydroxypropyl trimethylammonium chloride solution was added to the flask, and the flask was then sealed;
(4) Placing the conical flask in the step (3) into a constant-temperature water bath oscillator, and oscillating 24h at room temperature to enable 3-chloro-2-hydroxypropyl trimethylammonium chloride to be uniformly attached to the surface of the activated carbon;
(5) Placing the conical flask in the step (4) into a water bath kettle with the temperature of 50 ℃, then dropwise adding 5 mol/L NaOH solution into the conical flask, adjusting the pH of the solution to 11-12.5 to reach the pH required by the epoxy reaction, sealing the conical flask, and reacting 8 h;
(6) Taking out the conical flask in the step (5), cooling to room temperature, dropwise adding 5 mol/L HCl solution into the conical flask, adjusting the pH to be less than 7, and stopping cationization reaction;
(7) Filtering the mixture obtained in the step (6), repeatedly washing the modified activated carbon with absolute ethyl alcohol for a plurality of times, and then washing the activated carbon with deionized water until the pH value of washing water is neutral, so as to remove unreacted 3-chloro-2-hydroxypropyl trimethylammonium chloride;
(8) And (3) drying the modified activated carbon obtained in the step (7) in a 60 ℃ oven for 24h, taking out and cooling to room temperature to obtain the 3-chloro-2-hydroxypropyl trimethylammonium chloride modified activated carbon, and marking as QAC-1:10.
2. Performance study
SEM characterization is carried out on unmodified active carbon and the active carbon modified by the chloridized-1-methylquinoline obtained in the example 2, and the obtained SEM characterization graphs are respectively shown in figure 1 and figure 2.
As can be seen from fig. 1, the unmodified activated carbon surface was loose, uneven and had many fragments. As can be seen from FIG. 2, the surface of the activated carbon modified by the chloridized-1-methylquinoline is attached with a plurality of fluffy spherical particles which are generated chloridized-1-methylquinoline. As can be seen from FIG. 2, the synthesized substances are not separated from the surface of the activated carbon even though being washed by the absolute ethyl alcohol and the deionized water for a plurality of times, which indicates that the bonding force between the chloridized-1-methylquinoline and the surface of the activated carbon is strong, and the secondary pollution is not easy to be caused by separation from the surface of the activated carbon.
The adsorption kinetics experiment was used to evaluate the PFOA performance of activated carbon, activated carbon modified with 1-methylquinoline chloride prepared in examples 1 and 2, and activated carbon modified with 3-chloro-2-hydroxypropyl trimethylammonium chloride of comparative example. The specific steps are as follows,
(1) Preparing 50 mg/L of perfluorooctanoic acid solution by using a volumetric flask, and filling the solution into a plastic bottle for standby;
(2) Accurately weighing 50 mg activated carbon under different modification conditions in a 100 mL ground conical flask by using an analytical balance, accurately sucking 50 mL perfluoro caprylic acid solution in the conical flask by using a pipette, and sealing;
(3) Placing the conical flask into a water bath constant temperature oscillator, and reacting at room temperature; every 12 th h, supernatant 1 mL is taken in a 15 mL plastic tube, and excessive ammonia water is added to make perfluorooctanoic acid completely react to ammonium perfluorooctanoate;
(4) And measuring the concentration of ammonium perfluorooctanoate by adopting an ultraviolet spectrophotometry to further obtain the concentration of PFOA.
As can be seen from fig. 3, when the activated carbon is modified with positive charges on the surface, the adsorption capacity and adsorption rate of PFOA are better than those of the original activated carbon. The activated carbon modified with 1-methylquinoline of example 2 had more quinoline than example 1, i.e., more synthetic 1-methylquinoline was added, resulting in blocking of some of the micropores in the activated carbon of example 2, resulting in lower PFOA adsorption performance of the activated carbon of example 2 than that of example 1. Whereas the activated carbon modified with comparative example 3-chloro-2-hydroxypropyl trimethylammonium chloride has lower adsorption performance than the activated carbon obtained in examples 1 and 2 due to the steric hindrance effect caused by the long carbon chain of the quaternary ammonium salt.
Finally, it should be noted that the above examples are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution, and all such modifications and equivalents are included in the scope of the claims of the present invention.
Claims (6)
1. A surface modification method for making the surface of active carbon positive is characterized by comprising the following steps:
step 1: screening the activated carbon, cleaning with deionized water, and drying for later use;
step 2: soaking the activated carbon obtained in the step 1 in hydrochloric acid with the concentration of 1mol/L, washing with deionized water to be neutral, and drying to constant weight;
step 3: adding quinoline into the activated carbon obtained in the step 2; the ratio of the activated carbon to the quinoline is 1g: (0.5-3.5) mL, and slightly stirring for 0.5-1 h to enable the activated carbon to fully adsorb quinoline;
step 4: slowly adding concentrated hydrochloric acid into the mixture in the step 3, wherein the mole number of the added concentrated hydrochloric acid is 3-5 times that of quinoline, and slightly stirring for 0.5-1 h after the concentrated hydrochloric acid is added dropwise, so that the activated carbon fully adsorbs the concentrated hydrochloric acid;
step 5: distilling the activated carbon adsorbed with quinoline and concentrated hydrochloric acid obtained in the step 4 under reduced pressure at 45 ℃;
step 6: transferring the pasty activated carbon obtained in the step 5 into a hydrothermal reaction kettle, adding methanol, uniformly mixing, sealing, and reacting for 6-12h at 145-180 ℃; wherein, the mole number of the added methanol is 2-3 times of that of the quinoline;
step 7: after the reaction kettle is cooled, taking out the product in the reaction kettle, and distilling under reduced pressure at 70 ℃ to remove unreacted methanol;
step 8: repeatedly washing the activated carbon treated in the step 7 with absolute ethyl alcohol and deionized water respectively, and drying at 70 ℃ to obtain the activated carbon modified by the chloridized-1-methylquinoline;
the structural formula of the chloridized-1-methylquinoline is as follows:
2. the surface modification method for electropositive surface of activated carbon according to claim 1, wherein in step 1, activated carbon having a particle size of 20 to 60 mesh is selected.
3. The surface modification method for electropositive activated carbon surface according to claim 1, wherein in step 2, the soaking time is at least 24 hours.
4. The surface modification method for imparting positive electrical properties to an activated carbon surface according to claim 1, wherein in step 3, the activated carbon adsorbs quinoline at a temperature of not more than 50 ℃.
5. The surface modification method for electropositive surface of activated carbon according to claim 1, wherein in step 4, the adding speed of concentrated hydrochloric acid is 3mL/min to 9mL/min.
6. The method for surface modification of an activated carbon surface according to claim 5, wherein in step 7, distillation is performed under reduced pressure until the white substance is completely precipitated.
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Citations (14)
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