CN114682287B - Protonated iron carbon nitride composite material for sewage advanced treatment and preparation method and application thereof - Google Patents
Protonated iron carbon nitride composite material for sewage advanced treatment and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000011282 treatment Methods 0.000 title claims abstract description 28
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical class [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010865 sewage Substances 0.000 title claims abstract description 14
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 231100000719 pollutant Toxicity 0.000 claims abstract description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 12
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000000197 pyrolysis Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- 230000005588 protonation Effects 0.000 claims abstract description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 51
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 44
- 238000006731 degradation reaction Methods 0.000 abstract description 44
- 239000000463 material Substances 0.000 abstract description 29
- 230000004913 activation Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- HYYBABOKPJLUIN-UHFFFAOYSA-N mefenamic acid Chemical compound CC1=CC=CC(NC=2C(=CC=CC=2)C(O)=O)=C1C HYYBABOKPJLUIN-UHFFFAOYSA-N 0.000 description 3
- 229960003464 mefenamic acid Drugs 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229960005404 sulfamethoxazole Drugs 0.000 description 3
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 3
- 229960003500 triclosan Drugs 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- -1 4-ABZ Chemical compound 0.000 description 1
- SFIQXCAOXHXGHW-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;hydrate Chemical compound O.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 SFIQXCAOXHXGHW-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 206010006474 Bronchopulmonary aspergillosis allergic Diseases 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 208000006778 allergic bronchopulmonary aspergillosis Diseases 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229940039407 aniline Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the technical field of sewage treatment, relates to the technical field of pollutant-containing wastewater treatment, and in particular relates to a protonated iron carbon nitride composite material for sewage deep treatment, and a preparation method and application thereof. According to the invention, firstly, a nitrogen-containing carbon source, oxalic acid and ferric salt are uniformly ground and then subjected to pyrolysis treatment, then a precursor sample is obtained through cooling, washing and drying, and the precursor sample is subjected to protonation treatment, and then is washed and dried to obtain the protonated iron-carbon nitride composite material. The method has the advantages of low-cost and easily-obtained raw materials and simple preparation process, and the prepared protonated iron carbon nitride material has the advantages of high catalytic activity, wide pH application range, strong resistance to water quality matrixes and the like, can greatly improve the activation effect of the peroxymonosulfate or the hydrogen peroxide, realize the efficient degradation of micro pollutants, solve the problems that the existing activation technology is greatly interfered by water matrixes, the degradation of pollutants is incomplete, the utilization efficiency of the peroxymonosulfate is low and the like, and has great application potential.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, relates to the technical field of pollutant-containing wastewater treatment, and in particular relates to a protonated iron carbon nitride composite material for sewage deep treatment, and a preparation method and application thereof.
Background
The microcontact is a novel pollutant in the environment, mainly comprises medicines, pesticides, personal care products, endocrine disruptors and the like, has the characteristics of wide pollution range, multiple types, long half life, high toxicity and the like, has the risks of carcinogenesis, teratogenesis and mutagenesis, has the potential and accumulation property to a certain extent, and can possibly damage the reproductive system of people and animals. The water circulation is used as a tie for connecting the circulation, and micro pollutants with different concentration levels are detected in the water environment, and the micro pollutants have non-negligible influence on the aquatic environment and the ecological balance of the water. Therefore, the removal of micro-pollutants in water environments is receiving increasing attention.
In recent years, persulfate has been widely used for degradation and removal of pollutants due to the advantages of relatively stability, convenient transportation, capability of generating high-activity sulfate radicals, and the like. When the persulfate is adopted to degrade the pollutants, the persulfate needs to be activated, and the traditional activation technology generally breaks oxygen bonds of the persulfate through UV, electrochemistry, hydroxylamine and the like to generate active species such as high-activity sulfate radicals, so that the degradation and removal of the pollutants are realized. The concentration of micro-pollutants in actual water is generally in the range of ng/L-mug/L, while the chloride ions (Cl) widely existing in natural water - ) Sulfate ion (SO) 4 2- ) Carbonate ion (CO) 3 2- ) Bicarbonate ion (HCO) 3 - ) The concentration of Natural Organic Matters (NOM) and the like is generally in the mg/L level, and the reaction rate of the water quality matrix and active species such as sulfate radical and the like is extremely fast and can reach 10 6 -10 9 mol -1 s -1 . Therefore, when the persulfate is used for advanced oxidative degradation of micro-pollutants in the water body, the coexisting water quality matrix in the water body can quench a large amount of active species such as sulfate radicals generated in the system, and the efficiency of oxidative degradation of the pollutants in a radical way is obviously inhibited. In addition, the water matrix may react with free radicals generated in the advanced oxidation process to generate byproducts with higher toxicity, thereby limiting the application of the water matrix in water.
Therefore, it is necessary and important to develop an activating material which is low in cost, green, efficient and strong in resistance to water body matrix interference so as to improve the activating effect of persulfate and the degradation efficiency of persulfate on pollutants.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a protonated iron-carbon nitride composite material for sewage advanced treatment and a preparation method thereof, and the material can solve the problems that the existing activation technology is greatly interfered by water matrixes, pollutants are not thoroughly degraded, the utilization efficiency of peroxymonosulfate is low and the like.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the invention provides a preparation method of a protonated iron carbon nitride composite material, which specifically comprises the following steps: and (3) uniformly grinding a nitrogen-containing carbon source, oxalic acid and ferric salt, performing pyrolysis treatment, cooling, washing and drying to obtain a precursor sample, and washing and drying the precursor sample after protonizing to obtain the protonizing iron-carbon nitride composite material.
Preferably, the nitrogen-containing carbon source includes thiourea, urea and melamine, and the iron salt includes anhydrous ferric chloride and ferric nitrate. Further, the nitrogen-containing carbon source is urea, and the ferric salt is anhydrous ferric chloride.
The preparation method can prepare the protonated iron-carbon nitride composite material, and the preparation raw materials are cheap and easy to obtain, and the preparation process is simple. Meanwhile, the prepared protonated iron-carbon nitride composite material is a carrier containing protonated graphite-like carbon nitride and iron atoms combined with the carrier, wherein the protonated graphite-like carbon nitride is provided with protonated nitrogen atoms, and the iron atoms coordinate with the nitrogen atoms in the carrier to form Fe-N bonds.
Preferably, the adding mass ratio of the nitrogen-containing carbon source, oxalic acid and ferric salt is 15: (0.1-2): (0.01-0.2).
Preferably, the pyrolysis treatment is to heat up from room temperature to 450-600 ℃ at a heating rate of (4-6) DEG C/min, and to maintain at this temperature for 1-3 hours.
Preferably, the protonation treatment is to mix and stir the precursor sample with the mineral acid for 3-5 hours.
More preferably, the inorganic acid comprises hydrochloric acid, sulfuric acid and nitric acid, and the feed liquid ratio of the precursor sample to the inorganic acid is 100-300mg:1-4mL. Further, the hydrochloric acid is 20-100% hydrochloric acid.
Preferably, both of said washes are centrifugal washes.
Further, the washing after pyrolysis treatment is to centrifugally wash 3-5 times with ultrapure water and then centrifugally wash 1-3 times with ethanol, substances obtained after pyrolysis cooling are required to be uniformly mixed with washing liquid before each centrifugation, the revolution of each centrifugation is 7000-10000 revolutions, the centrifugation temperature is 4-25 ℃, and the centrifugation time is 3-10 minutes. The centrifugal washing after the protonation treatment is to firstly use ultrapure water for centrifugal washing 15-30 times, then use ethanol for centrifugal washing 1-3 times, and the substances obtained after the protonation treatment are required to be uniformly mixed with washing liquid before each centrifugation, the revolution of each centrifugation is 7000-10000 revolutions, the centrifugation temperature is 4-25 ℃, and the centrifugation time is 3-10min.
Preferably, the drying after pyrolysis treatment is to place the lower layer material obtained after centrifugal washing in a drying oven at a drying temperature of 40-80 ℃.
Preferably, the cooling treatment after the pyrolysis treatment is natural cooling to room temperature.
The invention also provides the protonated iron carbon nitride composite material prepared by the preparation method.
The invention also provides application of the protonated iron-carbon nitride composite material in sewage treatment.
Preferably, the wastewater is wastewater containing pollutants. Further, organic micro-pollutants in the pollutant-containing wastewater include, but are not limited to, bisphenol a (BPA), p-hydroxybenzoic acid (PHBA), p-chlorophenol (PCP), bisphenol a (BPA), p-chloroaniline (PCA), mefenamic acid (MFA), p-cyanoaniline (4-ABZ), sulfamethoxazole (SMX), aniline (aniline), triclosan (triclosan).
The protonated iron carbon nitride composite material catalyst provided by the invention has high catalytic activity on persulfate (peroxymonosulfate) and can activate hydrogen peroxide, so that the high-efficiency degradation of micro pollutants is realized, the pH value is not required to be regulated in the application process, the catalytic activity is not interfered by water quality matrixes, and the application range is wide.
The invention also provides a sewage advanced treatment method, namely, the protonated iron-carbon nitride composite material and the peroxymonosulfate or the hydrogen peroxide are put into sewage to be treated together, and the aim of degrading pollutants in water is achieved by activating the peroxymonosulfate or the hydrogen peroxide.
Preferably, the addition amount of the protonated iron-carbon nitride composite material is 0.1g/L, the addition amount of the peroxymonosulfate is 0.01-0.2mM, and the addition amount of the hydrogen peroxide is 0.2-2mM.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a protonated iron-carbon nitride composite material for sewage advanced treatment, which comprises the steps of firstly grinding a nitrogen-containing carbon source, oxalic acid and ferric salt uniformly, then carrying out pyrolysis treatment, cooling, washing and drying to obtain a precursor sample, carrying out protonation treatment on the precursor sample, and washing and drying to obtain the protonated iron-carbon nitride composite material. The method has the advantages of low-cost and easily-obtained raw materials, low production cost, simple preparation process, short preparation period, low requirements on equipment, good material stability and strong repeatability. The prepared protonated iron carbon nitride material has the advantages of high catalytic activity, wide pH application range, strong resistance to water quality matrix and the like, can greatly improve the activation effect of the peroxymonosulfate or hydrogen peroxide, realize the efficient degradation of micro pollutants, has lower leaching amount of material iron, can solve the problems that the prior activation technology is greatly interfered by the water body matrix, the degradation of the pollutants is incomplete, the utilization efficiency of the peroxymonosulfate is low and the like, and has great application potential.
Drawings
FIG. 1 is an XRD pattern of Protonated Carbon Nitride (PCN), protonated oxygen-doped carbon nitride (POCN), protonated iron-doped carbon nitride (PFeCN), and protonated iron-oxygen-doped carbon nitride (PFeOCN);
FIG. 2 is a graph showing the degradation profile of bisphenol A (BPA) by PCN, POCN, PFeCN and PFeOCN-activated PMS (degradation rate C t /C 0 Representation, C 0 For the concentration of microcontaminants before degradation, C t Is the concentration of the degraded micro-pollutants);
FIG. 3 is a graph showing the effect of PMS dose on PFeOCN material activated PMS degradation BPA;
FIG. 4 is a graph of the effect of the initial pH of a solution on PFeOCN material activated PMS degradation BPA;
FIG. 5 is a graph of the effect of aqueous substrates on PFeOCN material activated PMS degradation of BPA;
FIG. 6 is PFeOCN material activation H 2 O 2 Degradation profile for BPA;
fig. 7 is a graph showing the degradation effect of PFeOCN material activated PMS on various contaminants.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1 preparation method of protonated iron carbon nitride (PFeOCN) composite material
The specific preparation method comprises the following steps:
(1) Weighing 15g of urea in a mortar, grinding and stirring uniformly to obtain a substance a; weighing 15g of urea and 0.25g of anhydrous oxalic acid in a mortar, and grinding and stirring uniformly to obtain a substance b; weighing 15g of urea and 100mg of anhydrous ferric chloride in a mortar, and grinding and uniformly stirring to obtain a substance c; weighing 15g of urea, 0.25g of anhydrous oxalic acid and 100mg of anhydrous ferric chloride in a mortar, and grinding and stirring uniformly to obtain a substance d;
(2) Transferring the substances a, B, C and D into a 50mL crucible, covering a cover, wrapping tightly with thick aluminum foil paper, placing into a muffle furnace, heating to 500 ℃ from room temperature at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, centrifugally washing the cooled substances (after 5 times of centrifugal washing with ultrapure water, washing with absolute ethyl alcohol for 2 times, each time of centrifugal revolution is 9000 revolutions, the centrifugal temperature is 4 ℃ and the centrifugal time is 5 min), and finally drying at 60 ℃ for 24 hours to obtain substances A, B, C and D, respectively marked as CN, OCN, feCN, feOCN, and grinding for later use.
(3) Respectively weighing substances A, B, C and D, respectively, 150mg of substances A, B, C and D are respectively placed in a 5mL beaker, 2mL of 50% hydrochloric acid is added, after stirring is carried out for 4 hours, the mixed solution is subjected to centrifugal washing (firstly ultrapure water is subjected to centrifugal washing for 20 times, then absolute ethyl alcohol is subjected to washing for 2 times, the rotation number of each centrifugal is 9000 revolutions, the centrifugal temperature is 4 ℃, and the centrifugal time is 5 minutes). Finally, drying at 60 ℃ for 24 hours to obtain various substances which are respectively marked as PCN, POCN, PFeCN, PFeOCN, and grinding for later use.
As shown in fig. 1, only the peaks of graphite-like phase carbon nitride appear in the XRD patterns of PCN, POCN, pfeCN and PFeOCN, indicating that neither Fe nor O incorporation destroys the structure of graphite-like phase carbon nitride.
Example 2 PFeOCN composite activation PMS degradation of BPA (bisphenol A) in Water
The effect of PCN, POCN, PFeCN, PFeOCN on the degradation of BPA in 100mL of 2 μm aqueous BPA solution was examined under conditions of ph=7±0.2, solid-to-liquid ratio of carbon nitride material (PCN, POCN, PFeCN, PFeOCN) to aqueous BPA solution of 0.1g/L, addition amount of PMS of 0.2mM, activation temperature of 25 ℃, and degradation time of 15min, and the results are shown in fig. 2.
As shown in fig. 2, when no carbon nitride material is added, the degradation of BPA by pure PMS is 0 within 15 min; when PCN is added, BPA is degraded by 5% after 15min of reaction; when POCN is added, BPA is degraded by 10% after 15min of reaction; when PfeCN is added, BPA is almost completely degraded after 15 minutes of reaction; and when PFeOCN is added, complete degradation of BPA can be realized within 6 min. Indicating that the PFeOCN material is effective in optimization, the subsequent experiments can be performed using PFeOCN.
Example 3 influence factors of PFeOCN composite activated PMS on degradation of Water BPA
1) Effect of PMS dosage on degradation of BPA
The effect of different PMS addition amounts (0.01, 0.06, 0.1, 0.2 mM) on PFeOCN material activated PMS degradation BPA was examined in 100mL of 2 μM BPA aqueous solution at pH=7+ -0.2, solid-to-liquid ratio of PFeOCN to BPA aqueous solution of 0.1g/L, activation temperature of 25 ℃, degradation time of 15min, and the result is shown in FIG. 3.
As shown in FIG. 3, the PMS degradation rate of PFeOCN material activated PMS is obviously accelerated with the increase of PMS concentration in the range of 0.01-0.2mM of PMS addition amount, and when the PMS addition amount is 0.01mM, the PFeOCN material activated PMS can realize complete removal of BPA in 15 min. When the PMS addition concentration is more than 0.1mM, the rate of PMS degradation BPA activated by the PFeOCN material is basically kept stable along with the increase of the PMS concentration. In the system of degrading BPA by activating PMS with PFeOCN material, the material can activate and utilize trace PMS in aqueous solution, has relatively high sensitivity to PMS, and can improve the utilization rate of PMS.
2) Effect of initial pH of aqueous solution on degradation of BPA
Under the conditions that the solid-to-liquid ratio of PFeOCN to BPA aqueous solution is 0.1g/L, the PMS addition amount is 0.2mM, the activation temperature is 25 ℃, and the degradation time is 15min, the influence of the initial pH (3+/-0.2,5 +/-0.2,7 +/-0.2,9 +/-0.2, 11+/-0.2) of the aqueous solution on the PMS degradation of PFeOCN material activated PMS is examined in 100mL of 2 mu M BPA aqueous solution, and the experimental result is shown in figure 4.
As shown in fig. 4, the FeOCNH composite material activated PMS can efficiently degrade BPA within the range of pH=3-11, and can completely degrade BPA within 6min, which indicates that the PFeOCN material has a wide pH application range and can not regulate the pH of the system in practical application.
3) Effect of aqueous substrates on degradation of BPA
In an actual water body, a large amount of coexisting ions and natural organic matters are contained, and the degradation of micro pollutants can be greatly influenced by the existence of the matters. Thus, at pH=7.+ -. 0.2, solid to liquid ratio of PFeOCN to BPA aqueous solution 0.1g/L, PMS addition 0.2mM, activation temperature 25 ℃, degradation time 15min, coexisting ions (Cl - ，SO 4 2- ，NO 3 - ，HCO 3 - ，HPO 4 - ，ClO 4 - ，K + ，Ca 2+ ，Na + ，Mg 2+ ) At a concentration of 50mM, natural Organic Matter (NOM) concentration of 20mgC/L (against an aqueous solution free of coexisting ions and natural organic matter) in 100mL of a 2 μm aqueous solution of BPAThe influence of water matrix in water environment on PFeOCN material activated PMS degradation BPA is examined, and the experimental result is shown in figure 5.
As shown in FIG. 5, complete degradation of BPA was achieved substantially within 6 minutes in the presence of various aqueous substrates. But within 4min, HCO compared with the control group 3 - And Mg (magnesium) 2+ Has a relatively small effect on the degradation of BPA. In general, the existence of the water quality matrix does not greatly influence the degradation of BPA by PFeOCN material activated PMS, which indicates that the PFeOCN material activated PMS has relatively high anti-interference capability for degrading BPA.
EXAMPLE 4 PFeOCN composite activated Hydrogen peroxide (H 2 O 2 ) Degrading BPA in water
At pH=7.+ -. 0.2, the solid-to-liquid ratio of PFeOCN to BPA aqueous solution is 0.1g/L, H 2 O 2 FeOCNH composite material activation H is inspected in 100mL of 2 mu M BPA aqueous solution under the conditions that the addition amount is 0.2mM, 0.5mM, 1mM and 2mM, the activation temperature is 25 ℃ and the degradation time is 15min 2 O 2 The results of the experiment on the degradation of BPA in water are shown in fig. 6.
As shown in FIG. 6, H follows within 15min 2 O 2 Concentration enhancement, PFeOCN material catalysis H 2 O 2 The higher the efficiency of degrading BPA, when H 2 O 2 At a concentration of 0.2mM, BPA degraded 63% in 15 min; when H is to 2 O 2 When the concentration of BPA is increased to 2mM, the BPA can be degraded by 91% in 15min, which indicates that the PFeOCN material is also suitable for activating H 2 O 2 A system.
Example 5 PFeOCN composite activated PMS degradation of multiple pollutants in Water
The degradation of the activated PMS of the FeOCNH composite material on various pollutants in water was examined in 100mL of a 2 μm aqueous solution of various pollutants (PHBA, PCP, ABPA, PCA, MFA, 4-ABZ, SMX, aniline, triclosan) at pH=7+ -0.2, a solid-to-liquid ratio of PFeOCN to aqueous BPA solution of 0.1g/L, an addition amount of PMS of 0.2mM, an activation temperature of 25℃and a degradation time of 15min, and the experimental results are shown in FIG. 7.
As shown in FIG. 7, the PFeOCN composite activated PMS can degrade various pollutants in water within 15min, and the degradation efficiency is more than 90%, which indicates that the PFeOCN composite activated PMS can degrade various micro pollutants, not only BPA.
In conclusion, the protonic iron-carbon nitride composite material catalyst (PFeOCN) prepared by the invention can efficiently activate PMS and also can efficiently activate H 2 O 2 The pH value range is relatively wide, the anti-interference capability to most water quality matrixes such as coexisting ions and natural organic matters is relatively high, and the anti-interference agent can be applied to degradation of various micro pollutants and has great practical application potential.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (4)
1. The application of the protonated iron-carbon nitride composite material in the treatment of bisphenol A-containing sewage is characterized in that the protonated iron-carbon nitride composite material and the peroxymonosulfate are put into the sewage to be treated together, and the aim of degrading pollutants in the water is achieved by activating the peroxymonosulfate, wherein the sewage contains the pollutant bisphenol A; the preparation method of the protonated iron carbon nitride composite material comprises the following steps: uniformly grinding a nitrogen-containing carbon source, oxalic acid and ferric salt, performing pyrolysis treatment, cooling, washing and drying to obtain a precursor sample, and washing and drying the precursor sample after protonizing to obtain a protonizing iron-carbon nitride composite material; the nitrogen-containing carbon source is selected from thiourea, urea or melamine, and the ferric salt is selected from anhydrous ferric chloride or ferric nitrate; the pyrolysis treatment is that the temperature is raised from room temperature to 450-600 ℃ at the temperature raising speed of (4-6) DEG C/min, and the pyrolysis treatment is kept at the temperature for 1-3h; the protonation treatment is to mix and stir the precursor sample with inorganic acid for 3-5h, wherein the inorganic acid is selected from hydrochloric acid, sulfuric acid or nitric acid.
2. The use according to claim 1, wherein the addition mass ratio of the nitrogen-containing carbon source, oxalic acid and ferric salt is 15: (0.1-2): (0.01-0.2).
3. The use according to claim 1, wherein the feed liquid ratio of the precursor sample to the mineral acid is 100-300mg:1-4mL.
4. The use according to claim 1, wherein the amount of the protonated iron carbon nitride composite material is 0.1g/L and the amount of the peroxymonosulfate is 0.01-0.2mM.
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| CN115608392B (en) * | 2022-08-05 | 2024-02-02 | 广东工业大学 | Persulfate catalytic material and preparation method and application thereof |
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