CN115970635A - Modified attapulgite-based adsorption material and preparation method thereof - Google Patents
Modified attapulgite-based adsorption material and preparation method thereof Download PDFInfo
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 159
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 159
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000001179 sorption measurement Methods 0.000 title abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 32
- 239000002689 soil Substances 0.000 claims abstract description 27
- 229920001661 Chitosan Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims abstract description 15
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002509 fulvic acid Substances 0.000 claims abstract description 15
- 229940095100 fulvic acid Drugs 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 239000008367 deionised water Substances 0.000 claims description 55
- 229910021641 deionized water Inorganic materials 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 31
- 229940010698 activated attapulgite Drugs 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 230000009471 action Effects 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention relates to the technical field of adsorption material preparation methods, and provides a modified attapulgite-based adsorption material and a preparation method thereof, wherein attapulgite raw soil is used as a raw material and is subjected to a purification process to prepare attapulgite purified powder, and then chitosan is used as a biomass carbon source and is carbonized on the surface of the attapulgite by a hydrothermal carbonization method to prepare carbonized attapulgite, so that the surface of the attapulgite can be loaded with more oxygen-containing groups and amino groups, the adsorption rate of the attapulgite is improved, and metals such as chromium and the like can be better adsorbed and removed; secondly, the attapulgite is subjected to acid activation treatment by using the biochemical fulvic acid, so that the number of functional groups on the surface of the attapulgite can be increased, and the adsorption capacity of the attapulgite on heavy metals is increased; the adsorption material prepared by the invention can adsorb and remove heavy metals and can adsorb and filter organic pollutants, and has excellent market application prospect.
Description
Technical Field
The invention relates to the technical field of preparation methods of adsorbing materials, in particular to a modified attapulgite-based adsorbing material and a preparation method thereof.
Background
Environmental protection and sustainable development become the subjects of current social development, and under the premise of ensuring that the material has excellent performance, the carbon material attaches importance to environmental friendliness and realizes high-valued utilization of natural resources, thus becoming the research focus of the material field. In recent years, clay mineral/carbon composite adsorption materials have the characteristics of rich sources, controllable structure, stable performance and the like, and thus become one of the hot spots for research on carbon-based composite adsorption materials. The attapulgite is a natural water-containing magnesium-aluminum-rich silicate clay mineral, and the unique pore channel structure and the one-dimensional rod crystals make the attapulgite become an ideal adsorbing material and a carrier material. At present, the adsorption material prepared by taking the modified attapulgite as a raw material is widely applied, but the adsorption performance of a plurality of adsorption materials still does not achieve the ideal optimal effect, the adsorption range is narrow, the adsorption rate of one substance can be improved, and different pollutant source substances cannot be adsorbed and removed.
For example, the preparation method of the modified attapulgite adsorbing material disclosed in the Chinese patent No. CN201110127108.3 comprises the steps of firstly, modifying purified and acid-activated attapulgite by adopting an aminosilane coupling agent to introduce amino groups on the surface of the attapulgite; then, amino and excessive acrylate are subjected to Michael addition to introduce an ester group, the ester group is subjected to Michael addition with polyethylene polyamine or alcohol amine, the solvent and excessive reactant are removed through reduced pressure distillation, vacuum drying and grinding and sieving are carried out to obtain a finished product, and the polyethylene polyamine or alcohol amine compound is bonded to the surface of the attapulgite in a covalent bond mode, so that the adsorption performance of the attapulgite on metal ions is greatly improved. The modified attapulgite adsorbing material prepared by the preparation method can only adsorb metal particles, cannot adsorb and remove some organic pollutants, and has a narrow adsorption range.
Disclosure of Invention
Solves the technical problem
Aiming at the defects in the prior art, the invention provides a modified attapulgite-based adsorbing material and a preparation method thereof, which can effectively solve the problems of narrow adsorption range and poor adsorption performance of the adsorbing material in the prior art.
Technical scheme
In order to realize the purpose, the invention is realized by the following technical scheme:
the modified attapulgite-based adsorbing material comprises the following raw materials in parts by weight: 20-22 parts of carbonized attapulgite, 20-25 parts of acid activated attapulgite, 100-110 parts of ferric trichloride hexahydrate solution and 360-380 parts of deionized water;
the carbonized attapulgite is prepared by taking attapulgite purified powder and chitosan as raw materials, and the acid-activated attapulgite is prepared by taking the attapulgite purified powder as the raw material and activating with biochemical fulvic acid, wherein the attapulgite purified powder is prepared by taking attapulgite raw soil as the raw material and purifying.
Further, the purification process of the attapulgite purified powder comprises the following steps:
step1, according to 50:1, weighing attapulgite raw soil and a dispersing agent, pouring the attapulgite raw soil and the dispersing agent into deionized water with the mass of 8-10 times of that of the attapulgite raw soil and the dispersing agent, fully mixing, pouring the mixture into a resin ball milling tank, and carrying out ball milling for 20 hours by using agate balls as ball milling media;
step2, stirring the ball-milled system in the step1 to prepare a raw soil suspension, standing for 30min, absorbing supernatant by a siphoning method, then adding deionized water to the same water level, and repeating the operations of stirring, settling, standing and absorbing the supernatant for 2-3 times;
and 3, mixing the supernatant obtained in the step2, putting the mixture into an oven at 55-60 ℃ for drying, and grinding to obtain the purified attapulgite powder.
Still further, the dispersant in step1 is sodium hexametaphosphate.
Furthermore, the stirring speed in the step2 is 400-500r/min, and the stirring time is 2-3min.
Furthermore, the preparation method of the carbonized attapulgite comprises the following steps:
step one, according to 1:4, weighing attapulgite purified powder and chitosan according to the mass ratio, pouring the attapulgite purified powder and the chitosan into a conical flask, adding deionized water into the conical flask, and performing ultrasonic dispersion at 25 ℃ to prepare a suspension;
step two, pouring the suspension liquid obtained in the step one into a polytetrafluoroethylene reaction kettle, reacting for 24 hours in a high-temperature furnace at 180 ℃, and cooling to room temperature after reaction;
step three, centrifugally separating the suspension which is treated and cooled to room temperature in the step two in a high-speed centrifuge of 11000r/min for 10min, then repeatedly washing the precipitate by using absolute ethyl alcohol and deionized water until the pH value of the precipitate is neutral, and then carrying out suction filtration;
and step four, putting the solid obtained after the suction filtration in the step three into a drying oven for drying, and grinding into powder to obtain the carbonized attapulgite.
Furthermore, the mass of the deionized water in the first step is 15 times of the total amount of the attapulgite purified powder and the chitosan, the ultrasonic dispersion frequency in the first step is 28-30kHz, and the ultrasonic dispersion time is 15min.
Furthermore, the drying temperature in the drying oven in the fourth step is 58-60 ℃.
Further, the preparation method of the acid-activated attapulgite comprises the following steps:
step a, weighing 5 parts by weight of attapulgite purified powder, mixing the attapulgite purified powder with 100 parts by weight of deionized water, and then placing the mixture into a high-speed stirrer with the speed of 8000r/min for stirring for 15-18min to prepare a first mixed solution;
b, weighing 1-2 parts by weight of biochemical fulvic acid, dissolving in 100 parts by weight of deionized water to prepare a solution, then pouring the solution into the first mixed solution in the step a, and stirring for 12 hours in a high-speed stirrer at the rotating speed of 8000r/min to obtain a second mixed solution;
and c, pouring the second mixed solution obtained in the step b into a Buchner funnel for suction filtration, repeatedly washing the mixture for 3 to 4 times by using deionized water, placing the obtained solid filter cake into a vacuum drying oven at the temperature of between 60 and 65 ℃ for constant-temperature drying for 12 hours, and grinding the solid filter cake by using an agate mortar to obtain the acid-activated attapulgite.
Further, the concentration of the ferric trichloride hexahydrate solution is 0.45mol/L.
A preparation method of a modified attapulgite-based adsorbing material comprises the following steps;
step1, mixing the carbonized attapulgite and the acid-activated attapulgite in parts by weight, performing ball milling after mixing, and sieving by a 200-mesh sieve to obtain raw material powder;
step2, mixing the raw material powder with the deionized water in parts by weight to prepare a raw material suspension, adjusting the pH to 11 by using a sodium hydroxide solution, and then carrying out ultrasonic dispersion for 2 hours at the frequency of 26-28 kHz;
step3, heating the raw material suspension processed by the Step2 to 50 ℃, adding the ferric trichloride hexahydrate solution in parts by weight under the condition of rapid stirring, continuously stirring for 30min, placing in a water bath thermostat at 100 ℃ for heat preservation for 4-5h, cooling to room temperature after heat preservation, centrifuging and washing with deionized water, repeating for 3 times, drying and grinding at 80 ℃, and sieving with a 200-mesh sieve to obtain mixed powder;
and Step4, placing the mixed powder in the Step3 in a tubular furnace, and heating and calcining in a hydrogen atmosphere, wherein the calcining process is as follows: calcining at 150 ℃, 200 ℃, 300 ℃, 400 ℃ and 500 ℃ for 30min respectively, finally keeping the temperature at 600 ℃ for 1h, naturally cooling, calcining at 250 ℃ in air atmosphere for 30min, and cooling to room temperature to obtain the modified attapulgite-based adsorbing material.
Advantageous effects
The invention provides a modified attapulgite-based adsorbing material and a preparation method thereof, compared with the prior art, the modified attapulgite-based adsorbing material has the following beneficial effects:
1. according to the method, attapulgite raw soil is used as a raw material, and is subjected to a purification process to prepare attapulgite purified powder, then chitosan is used as a biomass carbon source and is carbonized on the surface of the attapulgite by a hydrothermal carbonization method to prepare carbonized attapulgite, so that more oxygen-containing groups and amino groups can be loaded on the surface of the attapulgite, the adsorption rate of the attapulgite is improved, metals such as chromium and the like can be better adsorbed and removed, no harmful gas is released in the preparation process of carbonized attapulgite, the preparation process is simple, and the preparation cost of an adsorbing material can be reduced to a certain extent; secondly, the attapulgite is subjected to acid activation treatment by using the biochemical fulvic acid, so that the number of functional groups on the surface of the attapulgite can be increased, and the adsorption capacity of the attapulgite on heavy metals is increased.
2. The invention takes carbonized attapulgite and acid activated attapulgite as raw materials, and compounds with ferric trichloride hexahydrate to prepare the adsorbing material, so that the prepared adsorbing material has strong magnetic performance and can be attracted by an electromagnetic field to achieve the aim of magnetic recovery; the adsorption material prepared by the invention can adsorb and remove heavy metals and can adsorb and filter organic pollutants.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. 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.
The present invention will be further described with reference to the following examples.
Example 1
The modified attapulgite-based adsorbing material comprises the following raw materials in parts by weight: 20 parts of carbonized attapulgite, 20 parts of acid-activated attapulgite, 100 parts of ferric chloride hexahydrate solution and 360 parts of deionized water;
the carbonized attapulgite is prepared from attapulgite purified powder and chitosan as raw materials, and the acid-activated attapulgite is prepared from attapulgite purified powder as raw material by activating with biochemical fulvic acid, wherein the attapulgite purified powder is prepared from attapulgite raw soil by purifying treatment.
The purification process of the attapulgite purified powder comprises the following steps:
step1, according to 50:1, weighing attapulgite raw soil and a dispersing agent, pouring the attapulgite raw soil and the dispersing agent into deionized water with the mass of 8 times of that of the attapulgite raw soil and the dispersing agent, fully mixing, pouring the mixture into a resin ball milling tank, and carrying out ball milling for 20 hours by using agate balls as ball milling media;
step2, stirring the ball-milled system in the step1 to prepare a raw soil suspension, standing for 30min, absorbing supernatant by a siphoning method, then adding deionized water to the same water level, and repeating the operations of stirring, settling, standing and absorbing the supernatant for 2 times;
and 3, mixing the supernatant obtained in the step2, drying in an oven at 55 ℃ after mixing, and grinding to obtain the purified attapulgite powder.
The dispersant in step1 is sodium hexametaphosphate.
The stirring speed in the step2 is 400r/min, and the stirring time is 2min.
The preparation method of the carbonized attapulgite comprises the following steps:
step one, according to 1:4, weighing attapulgite purified powder and chitosan according to the mass ratio, pouring the attapulgite purified powder and the chitosan into a conical flask, adding deionized water into the conical flask, and performing ultrasonic dispersion at 25 ℃ to prepare a suspension;
step two, pouring the suspension liquid obtained in the step one into a polytetrafluoroethylene reaction kettle, reacting for 24 hours in a high-temperature furnace at 180 ℃, and cooling to room temperature after the reaction;
step three, centrifugally separating the suspension which is treated and cooled to room temperature in the step two in a high-speed centrifuge of 11000r/min for 10min, then repeatedly washing the precipitate by using absolute ethyl alcohol and deionized water until the pH value of the precipitate is neutral, and then carrying out suction filtration;
and step four, putting the solid obtained after the suction filtration in the step three into a drying oven for drying, and grinding into powder to obtain the carbonized attapulgite.
The mass of the deionized water in the first step is 15 times of the total amount of the attapulgite purified powder and the chitosan, the ultrasonic dispersion frequency in the first step is 28kHz, and the ultrasonic dispersion time is 15min.
In the fourth step, the drying temperature in the drying oven is 58 ℃.
The preparation method of the acid-activated attapulgite comprises the following steps:
step a, weighing 5 parts by weight of attapulgite purified powder, mixing the attapulgite purified powder with 100 parts by weight of deionized water, and then placing the mixture into a high-speed stirrer with the speed of 8000r/min for stirring for 15min to prepare a first mixed solution;
b, weighing 1 part by weight of biochemical fulvic acid, dissolving the biochemical fulvic acid in 100 parts by weight of deionized water to prepare a solution, then pouring the solution into the first mixed solution in the step a, and stirring the solution in a high-speed stirrer at the rotating speed of 8000r/min for 12 hours to obtain a second mixed solution;
and c, pouring the second mixed solution obtained in the step b into a Buchner funnel for suction filtration, repeatedly washing the mixture for 3 times by using deionized water, placing the obtained solid filter cake into a vacuum drying oven at 60 ℃ for constant-temperature drying for 12 hours, and grinding the solid filter cake by using an agate mortar to obtain the acid-activated attapulgite.
The concentration of the ferric trichloride hexahydrate solution is 0.45mol/L.
A preparation method of a modified attapulgite-based adsorption material comprises the following steps;
step1, mixing the carbonized attapulgite and the acid-activated attapulgite in parts by weight, performing ball milling after mixing, and sieving by a 200-mesh sieve to obtain raw material powder;
step2, mixing the raw material powder with the deionized water in parts by weight to prepare a raw material suspension, adjusting the pH to 11 by using a sodium hydroxide solution, and then carrying out ultrasonic dispersion for 2 hours at the frequency of 26 kHz;
step3, heating the raw material suspension processed in Step2 to 50 ℃, adding the ferric trichloride hexahydrate solution in parts by weight under the condition of rapid stirring, continuously stirring for 30min, placing in a water bath thermostat at 100 ℃ for heat preservation for 4h, cooling to room temperature after heat preservation, centrifuging and washing with deionized water, repeating for 3 times, drying and grinding at 80 ℃, and sieving with a 200-mesh sieve to obtain mixed powder;
and Step4, placing the mixed powder in the Step3 in a tubular furnace, and heating and calcining in a hydrogen atmosphere, wherein the calcining process is as follows: calcining at 150 deg.C, 200 deg.C, 300 deg.C, 400 deg.C and 500 deg.C for 30min respectively, finally placing at 600 deg.C for 1h, naturally cooling, calcining at 250 deg.C for 30min in air atmosphere, and cooling to room temperature to obtain the modified attapulgite-based adsorbing material.
Example 2
The modified attapulgite-based adsorbing material comprises the following raw materials in parts by weight: 22 parts of carbonized attapulgite, 25 parts of acid-activated attapulgite, 110 parts of ferric trichloride hexahydrate solution and 380 parts of deionized water;
the carbonized attapulgite is prepared from attapulgite purified powder and chitosan as raw materials, and the acid-activated attapulgite is prepared from attapulgite purified powder as raw material by activating with biochemical fulvic acid, wherein the attapulgite purified powder is prepared from attapulgite raw soil by purifying treatment.
The purification process of the attapulgite purified powder comprises the following steps:
step1, according to 50:1, weighing attapulgite raw soil and a dispersing agent, pouring the attapulgite raw soil and the dispersing agent into deionized water with the mass being 10 times of that of the attapulgite raw soil and the dispersing agent, fully mixing, pouring the mixture into a resin ball milling tank, and carrying out ball milling for 20 hours by using agate balls as ball milling media;
step2, stirring the ball-milled system in the step1 to prepare a raw soil suspension, standing for 30min, absorbing supernatant by a siphoning method, then adding deionized water to the same water level, and repeating the operations of stirring, settling, standing and absorbing the supernatant for 3 times;
and 3, mixing the supernatant obtained in the step2, putting the mixture into a 60-DEG C oven for drying, and grinding to obtain the attapulgite purified powder.
The dispersant in step1 is sodium hexametaphosphate.
The stirring speed in the step2 is 500r/min, and the stirring time is 3min.
The preparation method of the carbonized attapulgite comprises the following steps:
step one, according to 1:4, weighing attapulgite purified powder and chitosan according to the mass ratio, pouring the attapulgite purified powder and the chitosan into a conical flask, adding deionized water into the conical flask, and performing ultrasonic dispersion at 25 ℃ to prepare a suspension;
step two, pouring the suspension liquid obtained in the step one into a polytetrafluoroethylene reaction kettle, reacting for 24 hours in a high-temperature furnace at 180 ℃, and cooling to room temperature after reaction;
step three, centrifugally separating the suspension which is treated and cooled to room temperature in the step two in a high-speed centrifuge of 11000r/min for 10min, then repeatedly washing the precipitate by using absolute ethyl alcohol and deionized water until the pH value of the precipitate is neutral, and then carrying out suction filtration;
and step four, putting the solid obtained after the suction filtration in the step three into a drying oven for drying, and grinding into powder to obtain the carbonized attapulgite.
In the first step, the mass of the deionized water is 15 times of the total amount of the attapulgite purified powder and the chitosan, the ultrasonic dispersion frequency in the first step is 30kHz, and the ultrasonic dispersion time is 15min.
In the fourth step, the drying temperature in the drying oven is 60 ℃.
The preparation method of the acid-activated attapulgite comprises the following steps:
step a, weighing 5 parts by weight of attapulgite purified powder, mixing the attapulgite purified powder with 100 parts by weight of deionized water, and then placing the mixture in a high-speed stirrer at 8000r/min for stirring for 18min to prepare a first mixed solution;
b, weighing 2 parts by weight of biochemical fulvic acid, dissolving the biochemical fulvic acid in 100 parts by weight of deionized water to prepare a solution, then pouring the solution into the first mixed solution in the step a, and stirring the solution in a high-speed stirrer at the rotating speed of 8000r/min for 12 hours to obtain a second mixed solution;
and c, pouring the second mixed solution obtained in the step b into a Buchner funnel for suction filtration, repeatedly washing the mixture for 4 times by using deionized water, placing the obtained solid filter cake into a vacuum drying oven at 65 ℃ for constant-temperature drying for 12 hours, and grinding the solid filter cake by using an agate mortar to obtain the acid-activated attapulgite.
The concentration of the ferric trichloride hexahydrate solution is 0.45mol/L.
A preparation method of a modified attapulgite-based adsorption material comprises the following steps;
step1, mixing the carbonized attapulgite and the acid-activated attapulgite in parts by weight, performing ball milling after mixing, and sieving by a 200-mesh sieve to obtain raw material powder;
step2, mixing the raw material powder with the deionized water in parts by weight to prepare a raw material suspension, adjusting the pH to 11 by using a sodium hydroxide solution, and then carrying out ultrasonic dispersion for 2 hours at the frequency of 28 kHz;
step3, heating the raw material suspension processed by the Step2 to 50 ℃, adding the ferric trichloride hexahydrate solution in parts by weight under the condition of rapid stirring, continuously stirring for 30min, placing in a water bath thermostat at 100 ℃ for heat preservation for 5h, cooling to room temperature after heat preservation, centrifuging and washing with deionized water, repeating for 3 times, drying and grinding at 80 ℃, and sieving with a 200-mesh sieve to obtain mixed powder;
and Step4, placing the mixed powder in the Step3 in a tubular furnace, and heating and calcining in a hydrogen atmosphere, wherein the calcining process is as follows: calcining at 150 ℃, 200 ℃, 300 ℃, 400 ℃ and 500 ℃ for 30min respectively, finally keeping the temperature at 600 ℃ for 1h, naturally cooling, calcining at 250 ℃ in air atmosphere for 30min, and cooling to room temperature to obtain the modified attapulgite-based adsorbing material.
Example 3
The modified attapulgite-based adsorbing material comprises the following raw materials in parts by weight: 21 parts of carbonized attapulgite, 23 parts of acid-activated attapulgite, 105 parts of ferric chloride hexahydrate solution and 370 parts of deionized water;
the carbonized attapulgite is prepared from attapulgite purified powder and chitosan as raw materials, and the acid-activated attapulgite is prepared from attapulgite purified powder as raw material by activating with biochemical fulvic acid, wherein the attapulgite purified powder is prepared from attapulgite raw soil by purification treatment.
The purification process of the attapulgite purified powder comprises the following steps:
step1, according to 50:1, weighing attapulgite raw soil and a dispersing agent according to the mass ratio, then pouring the attapulgite raw soil and the dispersing agent into deionized water with the mass being 9 times that of the attapulgite raw soil, fully mixing, pouring the mixture into a resin ball-milling tank, and carrying out ball milling by using agate balls as ball-milling media for 20 hours;
step2, stirring the ball-milled system in the step1 to prepare a raw soil suspension, standing for 30min, absorbing supernatant by a siphoning method, then adding deionized water to the same water level, and repeating the operations of stirring, settling, standing and absorbing the supernatant for 3 times;
and 3, mixing the supernatant obtained in the step2, putting the mixture into a 58 ℃ oven for drying, and grinding to obtain the attapulgite purified powder.
The dispersant in step1 is sodium hexametaphosphate.
The stirring speed in the step2 is 400r/min, and the stirring time is 3min.
The preparation method of the carbonized attapulgite comprises the following steps:
step one, according to 1:4, weighing attapulgite purified powder and chitosan according to the mass ratio, pouring the attapulgite purified powder and the chitosan into a conical flask, adding deionized water into the conical flask, and performing ultrasonic dispersion at 25 ℃ to prepare a suspension;
step two, pouring the suspension liquid obtained in the step one into a polytetrafluoroethylene reaction kettle, reacting for 24 hours in a high-temperature furnace at 180 ℃, and cooling to room temperature after reaction;
step three, centrifugally separating the suspension which is treated and cooled to room temperature in the step two in a high-speed centrifuge of 11000r/min for 10min, then repeatedly washing the precipitate by using absolute ethyl alcohol and deionized water until the pH value of the precipitate is neutral, and then carrying out suction filtration;
and step four, putting the solid obtained after the suction filtration in the step three into a drying oven for drying, and grinding into powder to obtain the carbonized attapulgite.
In the first step, the mass of the deionized water is 15 times of the total amount of the attapulgite purified powder and the chitosan, the ultrasonic dispersion frequency in the first step is 29kHz, and the ultrasonic dispersion time is 15min.
In the fourth step, the drying temperature in the drying oven is 59 ℃.
The preparation method of the acid activated attapulgite comprises the following steps:
step a, weighing 5 parts by weight of attapulgite purified powder, mixing the attapulgite purified powder with 100 parts by weight of deionized water, and then placing the mixture in a high-speed stirrer at 8000r/min for stirring for 17min to prepare a first mixed solution;
b, weighing 2 parts by weight of biochemical fulvic acid, dissolving the biochemical fulvic acid in 100 parts by weight of deionized water to prepare a solution, then pouring the solution into the first mixed solution in the step a, stirring the solution in a high-speed stirrer for 12 hours at the rotating speed of 8000r/min, and recording the solution as a second mixed solution;
and c, pouring the second mixed solution obtained in the step b into a Buchner funnel for suction filtration, repeatedly washing the mixture for 4 times by using deionized water, placing the obtained solid filter cake into a vacuum drying oven at the temperature of 62 ℃ for constant-temperature drying for 12 hours, and grinding the solid filter cake by using an agate mortar to obtain the acid-activated attapulgite.
The concentration of the ferric trichloride hexahydrate solution is 0.45mol/L.
A preparation method of a modified attapulgite-based adsorption material comprises the following steps;
step1, mixing the carbonized attapulgite and the acid-activated attapulgite in parts by weight, performing ball milling after mixing, and sieving by a 200-mesh sieve to obtain raw material powder;
step2, mixing the raw material powder with the deionized water in parts by weight to prepare a raw material suspension, adjusting the pH to 11 by using a sodium hydroxide solution, and then carrying out ultrasonic dispersion for 2 hours at the frequency of 27 kHz;
step3, heating the raw material suspension processed by the Step2 to 50 ℃, adding the ferric trichloride hexahydrate solution in parts by weight under the condition of rapid stirring, continuously stirring for 30min, placing in a water bath thermostat at 100 ℃ for heat preservation for 5h, cooling to room temperature after heat preservation, centrifuging and washing with deionized water, repeating for 3 times, drying and grinding at 80 ℃, and sieving with a 200-mesh sieve to obtain mixed powder;
and Step4, placing the mixed powder in the Step3 in a tubular furnace, and heating and calcining in a hydrogen atmosphere, wherein the calcining process is as follows: calcining at 150 deg.C, 200 deg.C, 300 deg.C, 400 deg.C and 500 deg.C for 30min respectively, finally placing at 600 deg.C for 1h, naturally cooling, calcining at 250 deg.C for 30min in air atmosphere, and cooling to room temperature to obtain the modified attapulgite-based adsorbing material.
Comparative example 1
The adsorbing material and the preparation method thereof provided by the comparative example are substantially the same as those of the example 1, and the main differences are as follows: the carbonized attapulgite in the raw material of the comparative example 1 is replaced by the purified attapulgite powder.
Comparative example 2
The adsorbing material and the preparation method thereof provided by the comparative example are substantially the same as those of the example 2, and the main differences are as follows: comparative example 2 the acid-activated attapulgite in the raw material was replaced by purified attapulgite powder.
Comparative example 3
The adsorbing material and the preparation method thereof provided by the comparative example are substantially the same as those of the example 3, and the main differences are as follows: comparative example 3 the carbonized attapulgite and the acid-activated attapulgite in the raw material were both replaced by purified attapulgite powder.
Performance testing
The adsorbing materials obtained by examples 1 to 3 of the present invention were respectively referred to as examples 1 to 3; the adsorbents prepared by comparative examples 1-3 were noted as comparative examples 1-3, and then the relevant performance tests were performed on examples 1-3 and comparative examples 1-3, and the data obtained are reported in the following table:
the data in the table show that the adsorption materials prepared in the examples 1 to 3 have higher heavy metal removal rate (such as chromium removal rate) compared with the comparative example 1, which indicates that the adsorption materials have better heavy metal adsorption performance due to the addition of the carbonized attapulgite; compared with the comparative example 2, the adsorbing materials prepared in the embodiments 1 to 3 have higher comprehensive organic pollutant rate (such as phenol removal rate), which shows that the adsorbing material has better organic pollutant adsorption performance due to the addition of the acid-activated attapulgite, so that the adsorbing material prepared by the invention has more excellent adsorption performance and better market application prospect.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (10)
1. The modified attapulgite-based adsorbing material is characterized by comprising the following raw materials in parts by weight: 20-22 parts of carbonized attapulgite, 20-25 parts of acid activated attapulgite, 100-110 parts of ferric trichloride hexahydrate solution and 360-380 parts of deionized water;
the carbonized attapulgite is prepared by taking attapulgite purified powder and chitosan as raw materials, and the acid-activated attapulgite is prepared by taking the attapulgite purified powder as the raw material and activating with biochemical fulvic acid, wherein the attapulgite purified powder is prepared by taking attapulgite raw soil as the raw material and purifying.
2. The modified attapulgite-based adsorbing material according to claim 1, wherein the purification process of the purified attapulgite powder comprises the following steps:
step1, according to 50:1, weighing attapulgite raw soil and a dispersing agent, pouring the attapulgite raw soil and the dispersing agent into deionized water with the mass of 8-10 times of that of the attapulgite raw soil and the dispersing agent, fully mixing, pouring the mixture into a resin ball milling tank, and carrying out ball milling for 20 hours by using agate balls as ball milling media;
step2, stirring the ball-milled system in the step1 to prepare a raw soil suspension, standing for 30min, absorbing supernatant by a siphoning method, then adding deionized water to the same water level, and repeating the operations of stirring, settling, standing and absorbing the supernatant for 2-3 times;
and 3, mixing the supernatant obtained in the step2, putting the mixture into an oven at 55-60 ℃ for drying, and grinding to obtain the purified attapulgite powder.
3. The modified attapulgite-based adsorbing material according to claim 2, wherein the dispersant in the step1 is sodium hexametaphosphate.
4. The modified attapulgite-based adsorbing material according to claim 2, wherein the stirring speed in the step2 is 400-500r/min, and the stirring time is 2-3min.
5. The modified attapulgite-based adsorbing material according to claim 1, wherein the preparation method of the carbonized attapulgite comprises the following steps:
step one, according to 1:4, weighing attapulgite purified powder and chitosan according to the mass ratio, pouring the attapulgite purified powder and the chitosan into a conical flask, adding deionized water into the conical flask, and performing ultrasonic dispersion at 25 ℃ to prepare a suspension;
step two, pouring the suspension liquid obtained in the step one into a polytetrafluoroethylene reaction kettle, reacting for 24 hours in a high-temperature furnace at 180 ℃, and cooling to room temperature after reaction;
step three, centrifugally separating the suspension which is treated and cooled to room temperature in the step two in a high-speed centrifuge of 11000r/min for 10min, then repeatedly washing the precipitate by using absolute ethyl alcohol and deionized water until the pH value of the precipitate is neutral, and then carrying out suction filtration;
and step four, putting the solid obtained after the suction filtration in the step three into a drying oven for drying, and grinding into powder to obtain the carbonized attapulgite.
6. The modified attapulgite-based adsorbing material according to claim 5, wherein the mass of the deionized water in the first step is 15 times of the total amount of the purified attapulgite powder and the chitosan, the ultrasonic dispersion frequency in the first step is 28-30kHz, and the ultrasonic dispersion time is 15min.
7. The modified attapulgite-based adsorbing material according to claim 5, wherein the drying temperature in the drying oven in the fourth step is 58-60 ℃.
8. The modified attapulgite-based adsorbing material according to claim 1, wherein the preparation method of the acid-activated attapulgite comprises the following steps:
step a, weighing 5 parts by weight of attapulgite purified powder, mixing the attapulgite purified powder with 100 parts by weight of deionized water, and then placing the mixture in a high-speed stirrer at 8000r/min for stirring for 15-18min to prepare a first mixed solution;
b, weighing 1-2 parts by weight of biochemical fulvic acid, dissolving in 100 parts by weight of deionized water to prepare a solution, then pouring the solution into the first mixed solution in the step a, and stirring for 12 hours in a high-speed stirrer at the rotating speed of 8000r/min to obtain a second mixed solution;
and c, pouring the second mixed solution obtained in the step b into a Buchner funnel for suction filtration, repeatedly washing the second mixed solution for 3 to 4 times by using deionized water, placing the obtained solid filter cake into a vacuum drying oven at the temperature of between 60 and 65 ℃ for constant-temperature drying for 12 hours, and grinding the solid filter cake by using an agate mortar to obtain the acid-activated attapulgite.
9. The modified attapulgite-based adsorbing material according to claim 1, wherein the concentration of the ferric trichloride hexahydrate solution is 0.45mol/L.
10. The preparation method of the modified attapulgite-based adsorbing material according to any one of claims 1 to 9, characterized in that the preparation method comprises the following steps;
step1, mixing the carbonized attapulgite and the acid-activated attapulgite in parts by weight, performing ball milling after mixing, and sieving by a 200-mesh sieve to obtain raw material powder;
step2, mixing the raw material powder with the deionized water in parts by weight to prepare a raw material suspension, adjusting the pH to 11 by using a sodium hydroxide solution, and then carrying out ultrasonic dispersion for 2 hours at the frequency of 26-28 kHz;
step3, heating the raw material suspension processed by the Step2 to 50 ℃, adding the ferric trichloride hexahydrate solution in parts by weight under the condition of rapid stirring, continuously stirring for 30min, placing in a water bath thermostat at 100 ℃ for heat preservation for 4-5h, cooling to room temperature after heat preservation, centrifuging and washing with deionized water, repeating for 3 times, drying and grinding at 80 ℃, and sieving with a 200-mesh sieve to obtain mixed powder;
and Step4, placing the mixed powder in the Step3 in a tubular furnace, and heating and calcining in a hydrogen atmosphere, wherein the calcining process is as follows: calcining at 150 deg.C, 200 deg.C, 300 deg.C, 400 deg.C and 500 deg.C for 30min respectively, finally placing at 600 deg.C for 1h, naturally cooling, calcining at 250 deg.C for 30min in air atmosphere, and cooling to room temperature to obtain the modified attapulgite-based adsorbing material.
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