CN113559914A - Metal/nitrogen-doped porous carbon catalyst for treating organic wastewater and preparation method thereof - Google Patents
Metal/nitrogen-doped porous carbon catalyst for treating organic wastewater and preparation method thereof Download PDFInfo
- Publication number
- CN113559914A CN113559914A CN202110969713.9A CN202110969713A CN113559914A CN 113559914 A CN113559914 A CN 113559914A CN 202110969713 A CN202110969713 A CN 202110969713A CN 113559914 A CN113559914 A CN 113559914A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- nitrogen
- metal
- solution
- organic wastewater
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 62
- 239000002184 metal Substances 0.000 title claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 229920001661 Chitosan Polymers 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000003929 acidic solution Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- -1 transition metal salt Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 54
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 20
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 14
- 229940043267 rhodamine b Drugs 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 12
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000005554 pickling Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 3
- OGQYJDHTHFAPRN-UHFFFAOYSA-N 2-fluoro-6-(trifluoromethyl)benzonitrile Chemical compound FC1=CC=CC(C(F)(F)F)=C1C#N OGQYJDHTHFAPRN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 229960003185 chlortetracycline hydrochloride Drugs 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 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 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- QYAPHLRPFNSDNH-MRFRVZCGSA-N (4s,4as,5as,6s,12ar)-7-chloro-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O QYAPHLRPFNSDNH-MRFRVZCGSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving chitosan in an acidic solution at room temperature to form a solution A, then dropwise adding the solution A into a sodium hydroxide solution to form a white precipitate, washing the white precipitate to be neutral, and drying to obtain modified chitosan; stirring and adsorbing a transition metal salt solution by using modified chitosan, and drying after adsorption to obtain a precursor; and placing the precursor in an activated gas atmosphere, heating and carbonizing, and then sequentially carrying out acid washing, washing and drying to obtain the metal/nitrogen-doped porous carbon catalyst for treating the organic wastewater. The invention also comprises the porous carbon material prepared by the method. The catalyst prepared by taking the modified chitosan as the carrier has good organic wastewater oxidative degradation activity and stability in Fenton-like reaction, and effectively solves the problems of low catalytic activity, poor stability and the like of the traditional Fenton-like catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation of functional porous carbon materials, and particularly relates to a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater and a preparation method thereof.
Background
Water, as a source of life, is one of the most important and irreplaceable resources among the existing resources. Preventing and controlling water pollution, ensuring the safety of drinking water, protecting and improving water environment and being beneficial to the masses. How to effectively remove toxic, harmful and difficultly biochemically degraded organic pollutants in industrial wastewater and domestic wastewater is one of the main environmental problems commonly faced by industries such as papermaking, leather, food, pesticides, petrifaction, pharmacy, textile, printing and dyeing, municipal administration and the like, is a necessary way for improving the cyclic utilization rate of water resources, and has important significance for optimizing a water supply structure, increasing water resource supply, relieving supply and demand contradictions, reducing water pollution and guaranteeing the ecological safety of water.
Has high toxicity,Of the numerous treatment methods for organic wastewater difficult to biochemically degrade, fenton's technology, a commonly mature advanced oxidation technology, has been used for organic wastewater treatment in engineering practice. The traditional Fenton technology refers to Fe under acidic condition2+Activation of H2O2Starting a free radical chain reaction to generate hydroxyl free radicals with high reaction activity, and further, under mild process conditions (normal pressure, 20-80 ℃), efficiently degrading organic pollutants which are high in toxicity and difficult to biochemically degrade in water without selectivity. However, the traditional Fenton technology has the defects that the pH operation window is narrow, the catalyst is difficult to recover, and a large amount of sludge and H are generated2O2Low utilization rate and the like.
Therefore, more and more researches are being made on the use of active metal components (Fe, Co, Ni, etc.) as metal oxides or metal-supported heterogeneous fenton-like catalysts for activating H2O2Generating hydroxyl free radicals to solve the problems of the traditional Fenton technology. In the metal-supported multiphase Fenton-like catalyst, a porous carbon material is most commonly used as a carrier, and the porous carbon material has the excellent properties of environmental friendliness, large specific surface area, developed pores, hydrothermal resistance, acid and alkali resistance, easiness in regulation and control of surface properties and the like, so that high dispersion and stable attachment of active metals can be realized. However, the problems of metal dissolution and poor catalyst stability of the traditional metal/porous carbon heterogeneous fenton-like catalyst cannot be completely avoided. Therefore, how to innovate a preparation method of the metal/porous carbon heterogeneous Fenton-like catalyst so as to improve the stable adhesion of an active metal component on the surface of the porous carbon becomes a key problem to be solved urgently when the metal-based heterogeneous Fenton-like catalyst is used for catalyzing, oxidizing and degrading organic pollutants.
Disclosure of Invention
Aiming at the problems of the traditional metal/porous carbon heterogeneous Fenton-like catalyst, the invention provides a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater and a preparation method thereof.
The preparation method of the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater comprises the following steps:
(1) dissolving chitosan in an acid solution at room temperature to form a solution A, then dropwise adding the solution A into a sodium hydroxide solution to form a white precipitate, washing the white precipitate with deionized water to be neutral, and drying to obtain modified chitosan;
(2) stirring and adsorbing a transition metal salt solution by using the modified chitosan obtained in the step (1), adsorbing for 12-36h, and drying to obtain a precursor;
(3) and (3) placing the precursor obtained in the step (2) in an activated gas atmosphere, heating and carbonizing at the speed of 5 ℃/min for 2-5h at the temperature of 700-1000 ℃, and then sequentially carrying out acid washing, washing and drying to obtain the metal/nitrogen-doped porous carbon catalyst for treating the organic wastewater.
Further, in the step (1), the acid solution is acetic acid, formic acid, hydrochloric acid or sulfuric acid, and the concentration of the acid solution is 2-6%.
Further, in the step (1), the mass ratio of the chitosan to the acidic solution is 1: 5-15.
Further, in the step (1), the volume ratio of the solution A to the sodium hydroxide solution is 1: 2-7.
Further, in the step (1), the concentration of the sodium hydroxide solution is 1-5 mol/L.
Further, in the step (2), the mass ratio of the modified chitosan to the transition metal salt solution is 1: 20-70.
Further, in the step (2), the transition metal salt solution is ferric sulfate, ferric chloride, ferric nitrate, nickel sulfate, nickel chloride, nickel nitrate, cobalt sulfate, cobalt nitrate, or cobalt chloride.
Further, the concentration of the transition metal salt solution is 10-200 g/L.
Further, in the step (3), acid washing is carried out for 12-48h in sulfuric acid solution, deionized water is used for washing until the solution is neutral, and then drying is carried out.
Further, in the step (3), acid washing is carried out for 12-48h in sulfuric acid solution, and the concentration of the sulfuric acid solution is 1-5 mol/L.
The metal/nitrogen-doped porous carbon catalyst for treating organic wastewater is prepared by the preparation method of the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater.
In summary, the invention has the following advantages:
1. according to the invention, the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater is used for modifying chitosan by a physical modification method, so that the chitosan has a strong adsorption effect on metal ions, and migration and dissolution of active metals can be avoided; by utilizing the characteristic that chitosan contains multiple nitrogen-containing functional groups, the multiple nitrogen-containing functional groups can be formed on the surface of porous carbon, and further a metal-nitrogen active center (M-N) is formedx) Enhancing the catalytic activity; the material is activated and pore-formed by carbon dioxide at high temperature, so that the catalytic reaction area can be increased, and the organic matter removal efficiency is improved; the subsequent acid washing can wash away the active metal aggregated on the surface, thereby obtaining the metal/nitrogen-doped porous carbon catalyst with high dispersity for treating the organic wastewater, and further enhancing the activity of the catalyst. The method is simple, convenient, quick and easy to operate.
2. The specific surface area of the metal/nitrogen co-doped porous carbon prepared by the preparation method can reach 400m2More than g, total pore volume of 1.46cm3More than g, and the pore diameter is intensively distributed at 2-10 nm. Under the acidic condition of pH 2, the removal rates of catalyzing persulfate and catalyzing hydrogen peroxide to oxidize and degrade rhodamine B can respectively reach 96.81% and 92.82%, and metal is not easy to lose, so that the method has good stability; while the removal rate of degrading rhodamine B by persulfate oxidation and hydrogen peroxide oxidation alone is only about 15 percent and 4 percent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a graph showing that metal/nitrogen co-doped porous carbon catalytic persulfate and hydrogen peroxide degraded rhodamine B with different Fe contents are prepared in example 1; wherein the oxidant in figure 1a is sodium persulfate, and the oxidant in figure 1b is hydrogen peroxide;
FIG. 2 is a graph of a graph showing that the preparation of the porous carbon catalytic persulfate and hydrogen peroxide degraded rhodamine B containing different transition metal salt metals/nitrogen codoped in example 2; wherein the oxidant in figure 2a is sodium persulfate and the oxidant in figure 2b is hydrogen peroxide;
FIG. 3 is a graph of a graph showing that metal/nitrogen co-doped porous carbon catalytic persulfate and hydrogen peroxide degraded rhodamine B prepared in example 3 at different pickling times; wherein the oxidant in figure 3a is sodium persulfate and the oxidant in figure 3b is hydrogen peroxide;
FIG. 4 is a graph showing the graphs of the metal/nitrogen co-doped porous carbon catalytic persulfate and the hydrogen peroxide degraded rhodamine B prepared in example 4 and having different carbonization temperatures; wherein the oxidant in fig. 4a is sodium persulfate, and the oxidant in fig. 4b is hydrogen peroxide;
FIG. 5 is a graph showing the degradation of different dyes by the metal/nitrogen co-doped porous carbon catalytic persulfate and hydrogen peroxide prepared in examples 1 to 4; wherein the oxidant in fig. 5a is sodium persulfate, and the oxidant in fig. 5b is hydrogen peroxide;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The preparation method of the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater comprises the following steps:
(1) dissolving chitosan in a 3% acetic acid solution at room temperature to form a solution A, then dropwise adding the solution A into a 1mol/L sodium hydroxide solution to form a white precipitate, washing the white precipitate with deionized water to be neutral, and drying to obtain modified chitosan; the volume ratio of the solution A to the sodium hydroxide solution is 3: 20;
(2) respectively stirring and adsorbing ferrous sulfate heptahydrate solutions of 20g/L, 40g/L, 80g/L, 100g/L and 200g/L by using the modified chitosan obtained in the step (1), adsorbing for 12 hours and drying to obtain a precursor; the mass ratio of the modified chitosan to the ferrous sulfate heptahydrate solution is 1: 50;
(3) respectively placing the precursors obtained in the step (2) in a carbon dioxide atmosphere, then heating and carbonizing at 850 ℃ at the speed of 5 ℃/min for 2h, then acid-washing in a 2mol/L sulfuric acid solution for 24h, washing with deionized water to neutrality, and drying to obtain the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater, wherein the names of the metal/nitrogen-doped porous carbon catalyst are respectively as follows: 20Fe @ CTS-850, 40Fe @ CTS-850, 80Fe @ CTS-850, 100Fe @ CTS-850, and 200Fe @ CTS-850.
Under the process conditions that the temperature is 50 ℃, the catalyst addition is 0.25 wt%, the addition of hydrogen peroxide and sodium Persulfate (PS) are 1 vt% and 0.1 wt%, the above 5 metal/nitrogen-doped porous carbon catalysts for treating organic wastewater are used for catalyzing persulfate and catalyzing hydrogen peroxide to oxidize and degrade rhodamine B wastewater respectively, and the corresponding experimental results are shown in figure 1.
Analysis experiment results show that with the increase of the Fe content, the activity of the catalyst is increased and then reduced in persulfate (figure 1a) and hydrogen peroxide (figure 1b) systems, and the reason may be that when the Fe content is low, the modified chitosan does not reach adsorption saturation, so that the number of active sites on the catalyst is small, and the activity of the catalyst is low; the excessive Fe can generate Fe agglomeration phenomenon in the subsequent carbonization process and can also cause the activity of the catalyst to be reduced, which indicates that when the concentration of ferrous sulfate is 40g/L, the modified chitosan reaches adsorption saturation, and the activity of the catalyst is the maximum at the moment.
Example 2
The preparation method of the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater comprises the following steps:
(1) dissolving chitosan in a 3% acetic acid solution at room temperature to form a solution A, then dropwise adding the solution A into a 1mol/L sodium hydroxide solution to form a white precipitate, washing the white precipitate with deionized water to be neutral, and drying to obtain modified chitosan; the volume ratio of the solution A to the sodium hydroxide solution is 3: 20;
(2) respectively stirring the modified chitosan obtained in the step (1) to adsorb 40g/L of FeSO4·7H2O、CoSO4·7H2O and NiSO4·6H2Adsorbing the O solution for 12 hours and then drying to obtain a precursor; the mass ratio of the modified chitosan to the metal sulfate solution is 1: 50;
(3) and (3) placing the precursor obtained in the step (2) in a carbon dioxide atmosphere, heating and carbonizing at the temperature of 850 ℃ at the speed of 5 ℃/min for 2h, then pickling in a sulfuric acid solution for 24h, washing with deionized water to be neutral, and drying to obtain the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater, wherein the names of the metal/nitrogen-doped porous carbon catalyst are 40Fe @ CTS-850, 40Co @ CTS-850 and 40Ni @ CTS-850.
Under the process conditions that the catalyst addition is 0.25 wt% and the addition of hydrogen peroxide and sodium Persulfate (PS) is 1 vt% and 0.1 wt% at 50 ℃, the above 3 metal/nitrogen-doped porous carbon catalysts for treating organic wastewater are respectively used for catalyzing persulfate and catalyzing hydrogen peroxide to oxidize and degrade rhodamine B wastewater, and the corresponding experimental results are shown in FIG. 2.
The analysis experiment result shows that the activity of the iron-containing catalyst is always superior to that of the cobalt-containing and nickel-containing catalysts in the process of catalyzing persulfate (figure 2a) and hydrogen peroxide (figure 2B) to decompose rhodamine B by different metals.
Example 3
The preparation method of the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater comprises the following steps:
(1) dissolving chitosan in 3 vt% acetic acid solution at room temperature to form solution A, then dropwise adding the solution A into 1mol/L sodium hydroxide solution to form white precipitate, washing the white precipitate with deionized water to be neutral, and drying to obtain modified chitosan; the volume ratio of the solution A to the sodium hydroxide solution is 3: 20;
(2) stirring the modified chitosan obtained in the step (1) to adsorb 40g/L ferrous sulfate heptahydrate solution, adsorbing for 12h, and drying to obtain a precursor; the mass ratio of the modified chitosan to the ferrous sulfate heptahydrate solution is 1: 50;
(3) and (3) placing the precursor obtained in the step (2) in a carbon dioxide atmosphere, heating and carbonizing at the temperature of 850 ℃ at the speed of 5 ℃/min for 2h, then respectively washing in sulfuric acid solution for 12h, 24h and 48h, washing with deionized water to neutrality, and drying to obtain the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater, which is respectively named as 40Fe @ CTS-12h, 40Fe @ CTS-24h and 40Fe @ CTS-36 h.
Under the process conditions of 50 ℃, the catalyst addition of 0.25 wt% and the addition of 1 vt% and 0.1 wt% of hydrogen peroxide and sodium Persulfate (PS) respectively, the metal/nitrogen-doped porous carbon catalyst for treating the organic wastewater is used for catalyzing persulfate and catalyzing hydrogen peroxide to oxidize and degrade rhodamine B wastewater, and the corresponding experimental result is shown in figure 3.
Analysis experiment results show that in the process of decomposing rhodamine B by catalyzing sodium persulfate (figure 3a) and hydrogen peroxide (figure 3B) with catalysts subjected to different pickling time lengths, the activity of the catalysts subjected to pickling for 24 hours is higher than that of the catalysts subjected to pickling for 12 hours and 36 hours, and the reason may be that iron on the surfaces of the catalysts is not completely washed away due to too short pickling time, and the active sites are less exposed, so that the activity of the catalysts is reduced; and the Fe dissolution phenomenon can occur under the strong acid environment if the pickling time is too long, so that the active sites are reduced, and the activity of the catalyst is reduced.
Example 4
The preparation method of the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater comprises the following steps:
(1) dissolving chitosan in 3 vt% acetic acid solution at room temperature to form solution A, then dropwise adding the solution A into 1mol/L sodium hydroxide solution to form white precipitate, washing the white precipitate with deionized water to be neutral, and drying to obtain modified chitosan; the volume ratio of the solution A to the sodium hydroxide solution is 3: 20;
the metal/nitrogen-doped porous carbon catalyst for treating the organic wastewater is used for treating the metal/nitrogen-doped porous carbon catalyst for treating the organic wastewater (2) the modified chitosan obtained in the step (1) is stirred to adsorb 40g/L ferrous sulfate heptahydrate solution, and the adsorption is carried out for 12 hours and then the solution is dried to obtain a precursor; the mass ratio of the modified chitosan to the ferrous sulfate heptahydrate solution is 1: 50;
(3) and (3) placing the precursor obtained in the step (2) in a carbon dioxide atmosphere, heating and carbonizing at the temperature of 700 ℃, 850 ℃ and 1000 ℃ at the speed of 5 ℃/min for 2h, pickling in a sulfuric acid solution for 24h, washing with deionized water to neutrality, and drying to obtain the metal/nitrogen-doped porous carbon catalyst for treating organic wastewater, which is named as 40Fe @ CTS-700, 40Fe @ CTS-850 and 40Fe @ CTS-1000 respectively.
Under the process conditions that the catalyst addition is 0.25 wt% and the addition of hydrogen peroxide and sodium Persulfate (PS) is 1 vt% and 0.1 wt% at 50 ℃, the above 3 metal/nitrogen-doped porous carbon catalysts for treating organic wastewater are respectively used for catalyzing persulfate and catalyzing hydrogen peroxide to oxidize and degrade rhodamine B wastewater, and the corresponding experimental results are shown in FIG. 4.
The analysis experiment results show that in the process of decomposing rhodamine B by catalyzing sodium persulfate (shown in figure 4a) and hydrogen peroxide (shown in figure 4B) with the catalyst after different pickling time lengths, compared with the calcination temperature of 700 ℃ and 1000 ℃, the catalyst has the highest activity when the calcination temperature is 850 ℃, the calcination temperature is increased, the specific surface area of the catalyst is increased, the active sites are increased, and the mass transfer effect is improved. However, too high a temperature causes Fe particles to agglomerate and cause cell collapse, resulting in a decrease in specific surface area, resulting in a decrease in activity of the catalyst.
Experimental example 1
Under the process conditions that the temperature is 50 ℃, the catalyst addition is 0.25 wt%, the addition of hydrogen peroxide and sodium Persulfate (PS) are 1 vt% and 0.1 wt%, organic wastewater such as rhodamine B, methylene blue, acid red, aureomycin hydrochloride, tetracycline hydrochloride and the like is degraded by catalyzing persulfate and hydrogen peroxide oxidation by using a metal/nitrogen-doped porous carbon catalyst (40Fe @ CTS-850) for treating the organic wastewater respectively.
As can be seen from fig. 5, in both persulfate (fig. 5a) and hydrogen peroxide (fig. 5b) systems, the obtained metal/nitrogen-doped porous carbon catalyst (40Fe @ CTS-850) for treating organic wastewater has good catalytic oxidative degradation effects on different organic matters, wherein the metal/nitrogen-doped porous carbon catalyst has good removal effects on methylene blue and acid red, and the removal rate of the metal/nitrogen-doped porous carbon catalyst reaches 95% or more when the reaction is carried out for 10 min; the method also has good removal effect on two antibiotics of chlortetracycline hydrochloride and tetracycline hydrochloride, and the removal rate of the chlortetracycline hydrochloride and the tetracycline hydrochloride is up to more than 95% after 1 hour of reaction.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (9)
1. A preparation method of a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater is characterized by comprising the following steps:
(1) dissolving chitosan in an acid solution at room temperature to form a solution A, then dropwise adding the solution A into a sodium hydroxide solution to form a white precipitate, washing the white precipitate with deionized water to be neutral, and drying to obtain modified chitosan;
(2) stirring and adsorbing a transition metal salt solution by using the modified chitosan obtained in the step (1), adsorbing for 12-36h, and drying to obtain a precursor;
(3) and (3) placing the precursor obtained in the step (2) in a carbon dioxide activated gas atmosphere, heating and carbonizing at the temperature of 700-1000 ℃ at the speed of 5 ℃/min for 2-5h, and then sequentially carrying out acid washing, washing and drying to obtain the metal/nitrogen-doped porous carbon catalyst for treating the organic wastewater.
2. The method for preparing a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater according to claim 1, wherein in the step (1), the acidic solution is acetic acid, formic acid, hydrochloric acid or sulfuric acid, and the concentration of the acidic solution is 2-6%.
3. The method for preparing a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater according to claim 1, wherein in the step (1), the mass ratio of the chitosan to the acidic solution is 1: 5-15.
4. The method for preparing a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater according to claim 1, wherein in the step (1), the volume ratio of the solution A to the sodium hydroxide solution is 1: 2-7.
5. The method for preparing a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater according to claim 1, wherein in the step (1), the concentration of the sodium hydroxide solution is 1-5 mol/L.
6. The method for preparing a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater according to claim 1, wherein in the step (2), the transition metal salt is ferric sulfate, ferric chloride, ferric nitrate, nickel sulfate, nickel chloride, nickel nitrate, cobalt sulfate, cobalt nitrate or cobalt chloride, and the concentration of the transition metal salt solution is 10-200 g/L.
7. The method for preparing a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater according to claim 1, wherein in the step (2), the mass ratio of the modified chitosan to the transition metal salt solution is 1: 20-70.
8. The method for preparing a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater according to claim 1, wherein in the step (3), the acid is washed in a sulfuric acid solution for 12-48h, and the concentration of the sulfuric acid solution is 1-5 mol/L.
9. The metal/nitrogen-doped porous carbon catalyst for treating organic wastewater prepared by the method for preparing a metal/nitrogen-doped porous carbon catalyst for treating organic wastewater according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110969713.9A CN113559914B (en) | 2021-08-23 | 2021-08-23 | Metal/nitrogen doped porous carbon catalyst for treating organic wastewater and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110969713.9A CN113559914B (en) | 2021-08-23 | 2021-08-23 | Metal/nitrogen doped porous carbon catalyst for treating organic wastewater and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113559914A true CN113559914A (en) | 2021-10-29 |
| CN113559914B CN113559914B (en) | 2023-10-13 |
Family
ID=78172421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110969713.9A Active CN113559914B (en) | 2021-08-23 | 2021-08-23 | Metal/nitrogen doped porous carbon catalyst for treating organic wastewater and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113559914B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100634A (en) * | 2021-12-14 | 2022-03-01 | 宁波碧城生态科技有限公司 | Preparation method, product and application of magnetic multi-component iron-carbon composite Fenton-like catalyst |
| CN115231684A (en) * | 2022-07-19 | 2022-10-25 | 东华大学 | Method for treating dye wastewater by using sludge hydrothermal biochar activated persulfate |
| CN116177614A (en) * | 2023-03-23 | 2023-05-30 | 科立鑫(珠海)新能源有限公司 | Technological method for reducing waste rate in cobalt oxide preparation process |
| CN116272990A (en) * | 2023-02-20 | 2023-06-23 | 浙江坤泽环境科技有限公司 | Preparation method and application of transition metal catalyst |
| CN116273126A (en) * | 2023-03-23 | 2023-06-23 | 天津大学 | Catalyst for degrading organic pollutants in wastewater and preparation method and application thereof |
| CN117776182A (en) * | 2024-02-23 | 2024-03-29 | 上海交通大学 | Preparation method and application of plant-derived porous carbon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276756A (en) * | 2011-07-29 | 2011-12-14 | 中国海洋大学 | Preparation method of chitosan hydroxybutyl derivative |
| CN111408392A (en) * | 2019-01-08 | 2020-07-14 | 南京理工大学 | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof |
-
2021
- 2021-08-23 CN CN202110969713.9A patent/CN113559914B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276756A (en) * | 2011-07-29 | 2011-12-14 | 中国海洋大学 | Preparation method of chitosan hydroxybutyl derivative |
| CN111408392A (en) * | 2019-01-08 | 2020-07-14 | 南京理工大学 | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| BASUDEV SAHOO等: "A Biomass-Derived Non-Noble Cobalt Catalyst for Selective Hydrodehalogenation of Alkyl and (Hetero)Aryl Halides" * |
| HANWEN YANG等: "Magnetic Fe3O4-N-doped carbon sphere composite for tetracycline degradation by enhancing catalytic activity for peroxymonosulfate: A dominant non-radical mechanism" * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100634A (en) * | 2021-12-14 | 2022-03-01 | 宁波碧城生态科技有限公司 | Preparation method, product and application of magnetic multi-component iron-carbon composite Fenton-like catalyst |
| CN114100634B (en) * | 2021-12-14 | 2023-11-10 | 宁波碧城生态科技有限公司 | Preparation method, product and application of magnetic multi-component iron-carbon composite Fenton-like catalyst |
| CN115231684A (en) * | 2022-07-19 | 2022-10-25 | 东华大学 | Method for treating dye wastewater by using sludge hydrothermal biochar activated persulfate |
| CN115231684B (en) * | 2022-07-19 | 2023-09-12 | 东华大学 | Method for treating dye wastewater by using sludge hydro-thermal biochar activated persulfate |
| CN116272990A (en) * | 2023-02-20 | 2023-06-23 | 浙江坤泽环境科技有限公司 | Preparation method and application of transition metal catalyst |
| CN116177614A (en) * | 2023-03-23 | 2023-05-30 | 科立鑫(珠海)新能源有限公司 | Technological method for reducing waste rate in cobalt oxide preparation process |
| CN116273126A (en) * | 2023-03-23 | 2023-06-23 | 天津大学 | Catalyst for degrading organic pollutants in wastewater and preparation method and application thereof |
| CN116177614B (en) * | 2023-03-23 | 2023-11-21 | 科立鑫(珠海)新能源有限公司 | Technological method for reducing waste rate in cobalt oxide preparation process |
| CN117776182A (en) * | 2024-02-23 | 2024-03-29 | 上海交通大学 | Preparation method and application of plant-derived porous carbon |
| CN117776182B (en) * | 2024-02-23 | 2024-05-03 | 上海交通大学 | Preparation method and application of plant-derived porous carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113559914B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113559914B (en) | Metal/nitrogen doped porous carbon catalyst for treating organic wastewater and preparation method thereof | |
| CN112206826B (en) | Preparation method and application of cobalt-iron alloy magnetic chitosan carbonized microsphere | |
| CN110124722A (en) | A kind of monatomic catalyst of nitrogen-doped carbon Base Metal and its preparation method and application | |
| CN106861695B (en) | A kind of preparation method and applications of magnetism anoxic position Copper ferrite catalyst | |
| CN111054417A (en) | High-efficiency iron monatomic Fenton catalyst, and synthesis method and application thereof | |
| CN107876053B (en) | High-strength wastewater treatment catalyst and preparation method and application thereof | |
| CN110694685A (en) | Preparation method and application of ferromanganese cobalt Prussian blue and manganese oxide composite nano-box assembled by ultrathin nano-sheets | |
| CN117772186B (en) | Cerium-manganese composite catalyst supported ceramic membrane and preparation method and application thereof | |
| CN111450829A (en) | Copper oxide nano catalytic film for catalyzing persulfate to degrade organic wastewater and preparation method thereof | |
| CN111072121B (en) | Preparation method and application of phenol degradation agent containing bimetallic oxide | |
| CN109173727A (en) | Failure complexing denitrfying agent regeneration method | |
| CN114558579B (en) | Catalyst for degrading organic pollutants in water and preparation method and application thereof | |
| Zhang | Preparation of heterogeneous catalysts based on CWAO technology | |
| CN112569968B (en) | Modified perovskite type catalyst and preparation method and application thereof | |
| CN111359675B (en) | Carboxymethyl chitosan doped polyaniline-MnFe2O4Spinel catalyst and preparation method and application thereof | |
| CN110508270B (en) | Magnesium oxide/carbon nanotube composite material and preparation method and application thereof | |
| CN114643058A (en) | Ternary nano alloy catalyst for decomposing hydrogen peroxide to generate hydroxyl radicals to degrade organic wastewater and preparation method thereof | |
| CN114225928A (en) | High-strength carbon-based heterogeneous catalyst and preparation method thereof | |
| CN110862126B (en) | Preparation method of hydrogel electrocatalytic electrode containing silver phosphate/calcium phosphate | |
| CN111495331B (en) | Strong acid heteroatom-resistant magnetic biochar water treatment agent and preparation method and application thereof | |
| CN114409028A (en) | Three-dimensional particle electrode for wastewater treatment and preparation method thereof | |
| CN113842942A (en) | Preparation and application of Fe-Ce-LDH/13X granular catalyst for heterogeneous electro-Fenton system | |
| Tennakone et al. | Nitrogen photoreduction by coprecipitated hydrous oxides of samarium (III) and vanadium (III) | |
| CN112608772A (en) | Method for removing organic sulfur in blast furnace gas | |
| CN113101958A (en) | Fe/Zn composite carbon-based catalyst, preparation method thereof and application of Fe/Zn composite carbon-based catalyst in activating persulfate to degrade organic matters in water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |