CN116809009A - Modified active coke based on ferromanganese valence state regulation and preparation method thereof - Google Patents
Modified active coke based on ferromanganese valence state regulation and preparation method thereof Download PDFInfo
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- 239000000571 coke Substances 0.000 title claims abstract description 114
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 31
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 27
- 229940099596 manganese sulfate Drugs 0.000 claims description 17
- 235000007079 manganese sulphate Nutrition 0.000 claims description 17
- 239000011702 manganese sulphate Substances 0.000 claims description 17
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 17
- WBZFUFAFFUEMEI-UHFFFAOYSA-M Acesulfame k Chemical compound [K+].CC1=CC(=O)[N-]S(=O)(=O)O1 WBZFUFAFFUEMEI-UHFFFAOYSA-M 0.000 claims description 16
- 229960004998 acesulfame potassium Drugs 0.000 claims description 13
- 235000010358 acesulfame potassium Nutrition 0.000 claims description 13
- 239000000619 acesulfame-K Substances 0.000 claims description 13
- 239000010865 sewage Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000004098 Tetracycline Substances 0.000 claims description 7
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 7
- 229960002180 tetracycline Drugs 0.000 claims description 7
- 229930101283 tetracycline Natural products 0.000 claims description 7
- 235000019364 tetracycline Nutrition 0.000 claims description 7
- 150000003522 tetracyclines Chemical class 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 2
- 238000007654 immersion Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 239000003344 environmental pollutant Substances 0.000 abstract description 16
- 231100000719 pollutant Toxicity 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 229960005164 acesulfame Drugs 0.000 description 5
- YGCFIWIQZPHFLU-UHFFFAOYSA-N acesulfame Chemical compound CC1=CC(=O)NS(=O)(=O)O1 YGCFIWIQZPHFLU-UHFFFAOYSA-N 0.000 description 5
- 238000009303 advanced oxidation process reaction Methods 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- 231100000049 endocrine disruptor Toxicity 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000008122 artificial sweetener Substances 0.000 description 1
- 235000021311 artificial sweeteners Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012546 transfer Methods 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of active coke treatment and application, and particularly relates to a modified active coke based on ferromanganese valence state regulation and a preparation method thereof. The modified active coke comprises main component active coke and active components, wherein the active components are immersed on the main component active coke, the active components comprise ferrous salt and divalent manganese salt, and the mass ratio of manganese to iron on the active coke is not higher than 20%. The modified active coke has the advantages of large specific surface area, high activity, wide pH application range and good adsorption and removal effects on novel pollutants in water; but also can activate persulfate to thoroughly oxidize novel organic pollutants into H 2 O and CO 2 The method comprises the steps of carrying out a first treatment on the surface of the After the modified active coke is saturated with the novel pollutant, the method can be carried out by throwingThe persulfate is added to remove the adsorbed novel pollutant effectively, so that the active coke can be regenerated in situ rapidly, the service cycle of the active coke is prolonged, and the use cost is reduced.
Description
Technical Field
The invention belongs to the technical field of active coke treatment and application, and particularly relates to a modified active coke based on ferromanganese valence state regulation and a preparation method thereof.
Background
The ubiquitous low concentration of new pollutants (Emerging pollutants, EPs) in industrial wastewater, town sewage, and natural bodies of water including sources of drinking water has posed a serious threat to human and water ecological health. These new pollutants include Pharmaceuticals and Personal Care Products (PPCPs), endocrine Disruptors (EDCs), persistent Organic Pollutants (POPs), artificial sweeteners (acs), and the like. EPs have stable structures, and are difficult to effectively remove by the conventional sewage treatment process, so that the treatment energy consumption is high, the cost is high and the efficiency is low. Removal of trace amounts of new contaminants on the order of ng/L- μg/L from town sewage and drinking water sources is an international scientific challenge.
The current adsorption and advanced oxidation processes (Advanced oxidation Processes, AOPs) are well-known techniques that can effectively treat lower concentrations of organics in water. The adsorption process can rapidly transfer new pollutants from the aqueous phase to the solid phase, but is limited in the practical water treatment process due to factors such as the use cost of the adsorbent. The advanced oxidation process can generate a large amount of strong oxidizing species such as hydroxyl free radicals (OH) and the like, can oxidize organic pollutants into carbon dioxide and water, and has the advantages of rapid reaction, high oxidation rate constant, wide application range, no secondary pollution and the like.
The carbon-based material catalyst has good adsorption and catalysis properties, and can avoid the problem of secondary pollution caused by leaching of heavy metals from the metal catalyst, so that the carbon-based material catalyst is often applied to adsorption and advanced oxidation processes. The active coke is active carbon with low specific surface area, which is mainly prepared by taking coal as raw material, and the specific surface area is generally less than or equal to 600m 2 And/g. Compared with wood activated carbon, the mesoporous proportion is higher, and the wood activated carbon has the advantages of relatively low price, high mechanical strength, wear resistance and the like. The specific surface area ratio of the activity Jiao Weikong to the mesoporous is 45% and 50%, and the corresponding ratio on the activated carbon is 95% and 5%, which indicates that the activity Jiao Jiekong has a developed structure and is not easy to block, and is beneficial to the adsorption and catalytic oxidation removal of novel pollutants with larger molecular weight. Therefore, the activated coke has unique advantages in the environment-friendly fields such as water treatment and the like based on the special pore structure and surface functional group properties of the activated coke.
In fact, however, activated coke is used as a carrier for industrial gas phase reaction catalysts and has not been widely studied and used in water treatment like activated carbon. It is worth mentioning that activated coke has been used in three-stage adsorption devices for deep purification of secondary effluent from sewage treatment plants in Zhengzhou, wherein the amount of activated Jiao Zhuangtian is up to tens of tons. Because the concentration of organic pollutants in the secondary effluent and micro-polluted organic matters such as novel pollutants are low, the adsorption capacity of the active coke is low, the active coke is easy to be saturated, the service cycle of the active coke is limited, the influence of industrial policies and the like is limited, the active coke is difficult to regenerate and recycle, and the use cost of the active coke is raised. Considering comprehensively, if the active coke is modified, the adsorption and removal capacity of the active coke on novel pollutants can be improved, the service life of the active coke can be prolonged, the rapid purification of the adsorbed novel pollutants by the persulfate catalyzed by the modified active coke and the in-situ regeneration can be realized, and the method is fundamental for greatly expanding the application range of the active coke.
Disclosure of Invention
Aiming at the defects and problems that the active coke has low adsorption capacity and is easy to saturate the active coke adsorption, so that the service cycle of the active coke is limited, the active coke is limited to the influence of industrial policies and the like, the active coke is difficult to regenerate and recycle, and the use cost of the active coke is raised in the water treatment due to the low concentration of organic pollutants, novel pollutants and other micro-polluted organic matters in secondary effluent, the invention provides a modified active coke based on ferromanganese valence state regulation and a preparation method thereof.
The invention solves the technical problems by adopting the scheme that: the modified active coke based on ferromanganese valence state regulation comprises main component active coke and active components, wherein the active components are immersed on the main component active coke, the active components comprise ferrous salt and divalent manganese salt, and the mass ratio of manganese to iron on the active coke is not higher than 20%.
The ferrous salt is any one of ferrous sulfate and ferrous chloride; the divalent manganese salt is any one of manganese sulfate, manganese chloride or manganese nitrate.
The modified active coke based on ferromanganese valence regulation, wherein the molar mass percentage of manganese sulfate is not less than 50%, and the molar mass percentage of ferrous sulfate is between 0 and 50%.
The modified active coke based on ferromanganese valence regulation is characterized in that the mass percentage of the active coke is more than 80%, and the mass percentage of the active component is less than 20%, wherein the mass percentage of the active component is calculated by manganese element and iron element.
The modified active coke based on ferromanganese valence state regulation has a specific surface area of 200-800 m 2 /g。
The invention also provides a preparation method of the modified active coke based on ferromanganese valence state regulation, which comprises the following steps:
preparing ferrous salt into ferrous salt solution, preparing divalent manganese salt into divalent manganese salt solution, and uniformly mixing the ferrous salt and the divalent manganese salt according to a proportion to prepare active component impregnating solution;
step two, placing the activity Jiao Jinzi in an active component impregnating solution, and placing the active component impregnating solution in a constant-temperature oscillator to oscillate for 24 hours under the condition of 120 r/min;
step three, pumping filtration and separation are carried out after the vibration is finished, and supernatant liquid is pumped out to obtain sediment;
step four, placing the precipitate in an oven, and drying for 12 hours at 70 ℃;
and fifthly, calcining at 300-700 ℃ for 1-5 hours after drying is finished, and obtaining the modified active coke.
According to the preparation method of the modified active coke based on ferromanganese valence state regulation, the active coke is sieved by a 100-mesh sieve in the second step.
The invention also provides application of the modified active coke based on ferromanganese valence regulation, and the modified active coke can effectively remove acesulfame potassium, tetracycline and methylene blue in wastewater or sewage.
According to the application, the modified active coke and the persulfate can be combined to effectively improve the removal effect of acesulfame and the like in wastewater or sewage.
The invention has the beneficial effects that: the modified active coke based on ferromanganese valence regulation, which is prepared by the invention, has the advantages of stable active coke yield of main component, excellent performance and relatively low price, has good adsorption and degradation effects on novel pollutants, and has wide development prospect.
The modified active coke based on ferromanganese valence state regulation, which is prepared by the invention, can activate persulfate, and for manganese or iron with lower valence state, persulfate can be activated to generate persulfate radical SO 4 - OH, superoxide radical O 2 - Singlet oxygen 1 O 2 And hole h + Equistrong oxidizing species capable of thoroughly oxidizing organic contaminants (e.g., acesulfame k) to H 2 O and CO 2 . Meanwhile, after the modified active coke adsorbs novel pollutants, the adsorbed novel pollutants are efficiently removed by adding persulfate, so that the active coke can be quickly regenerated in situ, the removing effect on acesulfame potassium in wastewater or sewage can be effectively improved, the service cycle of the active coke is prolonged, and the use cost is reduced.
The modified active coke prepared by the invention has the advantages of large specific surface area, high activity, wide pH application range and good adsorption and removal effects on novel pollutants in water.
The modified active coke based on ferromanganese valence regulation, which is prepared by the invention, can be produced by taking commercial active coke as a raw material, and can also be embedded into the existing active coke preparation process taking semi-coke as a raw material, thereby greatly reducing modification cost and use cost.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1: the embodiment provides a modified active coke based on ferromanganese valence regulation, which comprises active coke as a main component and an active component, wherein in the embodiment, only manganese sulfate is used as the active component, and ferrous salt is not used, wherein the active component manganese sulfate is immersed on the active coke.
The preparation method comprises the following steps:
firstly, adding 1.0g of manganese sulfate into 50mL of deionized water to prepare a manganese sulfate solution, so as to obtain an active component impregnating solution;
step two, after screening the active coke by a 100-mesh sieve, taking 2.5g of active coke powder to be immersed in a manganese sulfate solution, and then placing the solution in a constant-temperature oscillator to oscillate for 24 hours at 25 ℃ and the rotating speed of 120 r/min;
step three, pumping filtration and separation are carried out after the vibration is finished, and supernatant liquid is pumped out to obtain sediment;
step four, placing the precipitate in an oven, and drying for 12 hours at 70 ℃;
and fifthly, calcining for 1-3 hours at the temperature of 300-700 ℃ after drying, wherein the valence state of the manganese element changes along with the calcining temperature, the calcining time and the like, and the valence state of the manganese element changes from divalent to seven, so that the obtained finished product is regarded as the manganese modified active coke Mn-ACO.
Example 2: the embodiment provides a modified active coke based on ferromanganese valence regulation, which comprises active coke as a main component and an active component, wherein in the embodiment, only manganese sulfate is used as the active component, and ferrous salt is not used, wherein the active component manganese sulfate is immersed on the active coke.
The preparation method comprises the following steps:
firstly, adding 1.0g of manganese sulfate into 50mL of deionized water to prepare a manganese sulfate solution, so as to obtain an active component impregnating solution;
step two, after screening the active coke by a 100-mesh sieve, taking 2.5g of active coke powder to dip in a manganese sulfate solution, and oscillating for 24 hours in a constant-temperature oscillator at 25 ℃ and the rotating speed of 120 r/min;
and step three, pumping out supernatant liquid by using a suction filtration separation method, and placing the precipitate modified active coke in a 70 ℃ oven for drying for 12 hours for later use, wherein the dried Mn-ACO is pyrolyzed in a muffle furnace at 600 ℃ for 2 hours to obtain the modified active coke based on manganese valence state regulation.
Example 3: the embodiment provides a modified active coke based on ferromanganese valence state regulation, which comprises active coke as a main component, ferrous salt as an active component and divalent manganese salt as an active component, wherein the active component is immersed on the active coke, the ferrous salt is ferrous sulfate, and the divalent manganese salt is manganese sulfate.
In addition, ferrous salt can be ferrous chloride; the divalent manganese salt can also be manganese chloride or manganese nitrate, and the functions of manganese and iron are not affected.
The preparation method comprises the following steps:
adding 1.0g of manganese sulfate and 1.0g of ferrous sulfate into 50mL of deionized water to prepare a composite solution, so as to obtain an active component impregnating solution;
step two, after screening the active coke by a 100-mesh sieve, taking 2.0g of active coke powder to be immersed in a manganese sulfate solution, and then placing the solution in a constant-temperature oscillator to oscillate for 24 hours at the temperature of 25 ℃ and the rotating speed of 120 r/min;
step three, pumping filtration and separation are carried out after the vibration is finished, and supernatant liquid is pumped out to obtain sediment;
step four, placing the precipitate in an oven, and drying for 12 hours at 70 ℃;
and fifthly, after drying, pyrolyzing for 3 hours at 700 ℃ to obtain the modified active coke MnFe-ACO based on ferromanganese valence state regulation.
Test example 1: in this test example, 50mL of acesulfame potassium solution with an initial concentration of 10mg/L was set as 2 groups, 10mg of unmodified active coke and an equivalent amount of manganese modified active coke prepared in example 1 were added to the 2 groups of acesulfame potassium solutions at 25℃respectively, and after 24 hours, the adsorption capacity of acesulfame potassium in the two groups was measured by spectrophotometry.
The result shows that the unmodified active coke has no adsorption effect basically; the adsorption capacity of the manganese modified active coke prepared in the embodiment 1 is 19.7mg/g, which shows that the modified active coke treated by the method has a certain adsorption effect on acesulfame potassium.
Test example 2: in the test example, 4 groups of acesulfame solution (50 mL) with initial concentration of 10mg/L are arranged, and 10mg of active coke (test group 1), 0.3mmol/L of potassium persulfate (test group 2), 10mg of active coke plus 0.3mmol/L of potassium persulfate (test group 3) and 10mg of manganese modified active coke plus 0.3mmol/L of potassium persulfate (test group 4) pyrolyzed in the embodiment 2 at 600 ℃ are respectively added to the 4 groups of acesulfame solution; (wherein: 4.05mg of solid potassium peroxodisulfate was added to 50mL of the solution so that the concentration of potassium peroxodisulfate in the solution was 0.3 mmol/L).
After 120min, the removal rate of acesulfame potassium in the different experimental groups was determined, and the results are shown in table 1.
Table 1 results of acesulfame k removal from different treatment groups
From the results shown in table 1, compared with the use of the modified active coke and persulfate (experimental group 4), the use of the unmodified active coke and persulfate (experimental group 3) has better removal effect on acesulfame solution, which indicates that the combined action of the modified active coke and persulfate can effectively improve the removal effect on acesulfame in wastewater or sewage.
Test example 3: in this test example, 50mL of an acesulfame potassium solution (test group 1) having an initial concentration of 10mg/L was set, 10mg of the ferromanganese modified active coke MnFe-ACO prepared in example 3 was added to the acesulfame potassium solution at 25℃and the adsorption capacity of the ferromanganese modified active coke prepared in example 3 was 21.5mg/g as measured by spectrophotometry after 24 hours.
Simultaneously, 50mL of 1 group of tetracycline solution with initial concentration of 10mg/L (experimental group 2) and 50mL of 1 group of methylene blue solution with initial concentration of 10mg/L (experimental group 3) were set, 10mg of ferromanganese modified active coke MnFe-ACO prepared in example 3 was added to 2 groups of solutions at 25 ℃, and the removal rates of acesulfame potassium, tetracycline and methylene blue were calculated after 24 hours, and the results are shown in Table 2.
Table 2 results of acesulfame k, tetracycline and methylene blue removal from different treatment groups
As can be seen from Table 2, the iron-modified activated coke prepared by the invention has good removal effects on acesulfame potassium, tetracycline and methylene blue, wherein the removal effects on tetracycline and methylene blue are excellent.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. A modified active coke based on ferromanganese valence state regulation is characterized in that: comprises main component active coke and active components, wherein the active components are immersed on the main component active coke, the active components comprise ferrous salt and bivalent manganese salt, and the mass ratio of manganese to iron on the active coke is not higher than 20%.
2. The modified activated coke based on ferromanganese valence state control according to claim 1, wherein: the ferrous salt is any one of ferrous sulfate and ferrous chloride; the divalent manganese salt is any one of manganese sulfate, manganese chloride or manganese nitrate.
3. The modified activated coke based on ferromanganese valence state control according to claim 2, wherein: wherein the molar mass percentage of the manganese sulfate is not less than 50 percent, and the molar mass percentage of the ferrous sulfate is between 0 and 50 percent.
4. The modified activated coke based on ferromanganese valence state control according to claim 1, wherein: the mass percentage of the active coke is more than 80 percent, and the mass percentage of the active component is less than 20 percent, wherein the mass percentage of the active component is calculated by manganese element and iron element.
5. The modified activated coke based on ferromanganese valence state control according to claim 1, wherein: the specific surface area of the active coke is 200-800 m 2 /g。
6. The method for preparing the modified activated coke based on ferromanganese valence state control according to any one of claims 1 to 5, wherein the method comprises the following steps: the method comprises the following steps:
preparing ferrous salt into ferrous salt solution, preparing divalent manganese salt into divalent manganese salt solution, and uniformly mixing the ferrous salt and the divalent manganese salt according to a proportion to prepare active component impregnating solution;
step two, sieving the active coke, immersing the active coke in an active component immersion liquid, and oscillating the active coke in a constant-temperature oscillator for 24 hours under the condition of 120 r/min;
step three, pumping filtration and separation are carried out after the vibration is finished, and supernatant liquid is pumped out to obtain sediment;
step four, placing the precipitate in an oven, and drying for 12 hours at 70 ℃;
and fifthly, calcining at 300-700 ℃ for 1-5 hours after drying is finished, and obtaining the modified active coke.
7. The method for preparing the modified active coke based on ferromanganese valence state control according to claim 6, which is characterized in that: and step two, sieving the active coke through a 100-mesh sieve.
8. Use of a modified activated coke based on ferromanganese valence control according to any one of claims 1 to 5, characterized in that: the modified active coke can effectively remove acesulfame potassium, tetracycline and methylene blue in wastewater or sewage.
9. The use of modified activated coke based on ferromanganese valence state control according to claim 8, wherein: the active modified coke can be combined with persulfate to effectively improve the removal effect of acesulfame potassium in wastewater or sewage.
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