CN110040842B - Method for grafting redox mediator on surface of inorganic filler and application - Google Patents
Method for grafting redox mediator on surface of inorganic filler and application Download PDFInfo
- Publication number
- CN110040842B CN110040842B CN201910357677.3A CN201910357677A CN110040842B CN 110040842 B CN110040842 B CN 110040842B CN 201910357677 A CN201910357677 A CN 201910357677A CN 110040842 B CN110040842 B CN 110040842B
- Authority
- CN
- China
- Prior art keywords
- inorganic filler
- redox mediator
- mercaptopropyl
- organic solvent
- methyl
- 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.)
- Active
Links
- 239000011256 inorganic filler Substances 0.000 title claims abstract description 51
- 229910003475 inorganic filler Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 33
- -1 mercaptopropyl Chemical group 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- DWUCCPNOMFYDOL-UHFFFAOYSA-N propyl(sulfanyl)silicon Chemical compound CCC[Si]S DWUCCPNOMFYDOL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000010456 wollastonite Substances 0.000 claims description 18
- 229910052882 wollastonite Inorganic materials 0.000 claims description 18
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 239000004005 microsphere Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 244000028419 Styrax benzoin Species 0.000 claims description 8
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 8
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 8
- 229960002130 benzoin Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 235000019382 gum benzoic Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 claims description 2
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 claims description 2
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000000987 azo dye Substances 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 239000002351 wastewater Substances 0.000 abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 8
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- 125000004151 quinonyl group Chemical group 0.000 description 4
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- 239000002504 physiological saline solution Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical compound CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 241001147693 Staphylococcus sp. Species 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000003698 anagen phase Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- AQXYVFBSOOBBQV-UHFFFAOYSA-N 1-amino-4-hydroxyanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2N AQXYVFBSOOBBQV-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- IPWKIXLWTCNBKN-UHFFFAOYSA-N Madelen Chemical compound CC1=NC=C([N+]([O-])=O)N1CC(O)CCl IPWKIXLWTCNBKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 229960002313 ornidazole Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Chemical & Material Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention belongs to the field of water treatment, relates to the field of treatment of wastewater containing pollutants, and particularly relates to a method for grafting a redox mediator on the surface of an inorganic filler and application thereof. The method comprises the steps of reacting mercaptopropyl silane coupling agent with inorganic filler to obtain mercaptopropyl modified inorganic filler, and then carrying out mercapto-alkene click chemical reaction with an allyl-containing redox mediator to obtain the inorganic filler with a surface grafted with the redox mediator. The inorganic filler with the surface grafted with the redox mediator, which is obtained by the invention, can obviously accelerate the degradation of the azo dye, can be repeatedly used, has wide raw material sources, few reaction steps and low cost, does not need to use raw materials which are easy to generate toxic and harmful substances when being contacted with moisture, and can be widely used in the treatment of wastewater containing the azo dye and nitrate.
Description
Technical Field
The invention relates to the field of water treatment engineering, in particular to a method for grafting a redox mediator on the surface of an inorganic filler and application thereof.
Background
With the development of society and economy, the population is growing continuously, in order to meet the higher and higher requirements of people on industrial and agricultural products, a large amount of chemical substances are synthesized by artificial means, and the manufacture and the use of the chemical substances cause the discharge of a large amount of waste water containing heavy metals and pollutants difficult to biodegrade to enter the environments where animals, plants and human beings live, and finally cause serious harm to the human health and the whole ecological circle in the nature. Azo dyes are one of chemical substances difficult to biodegrade, and have become the most widely applied synthetic dyes with the largest using amount in the printing and dyeing process of textile clothes due to the characteristics of simple synthetic process, low cost, outstanding dyeing performance and the like. About 10-15% of the dye is lost to the printing waste water during the printing process, and the discharge of the printing waste water causes serious damage to the receiving water body, including azo dyes.
Nitrates are another class of chemicals that are highly harmful to humans and the environment. Ammonia nitrogen and nitrate nitrogen contained in excessively applied fertilizers, domestic sewage, excrement, industrial sewage and the like enter the natural environment through soil, water and the like, and are one of main substances for causing water eutrophication. The conventional biochemical treatment process can only convert ammonia nitrogen into nitrate nitrogen generally, and the reduction of the nitrate nitrogen cannot be efficiently completed in the general treatment process because the denitrification efficiency is low.
Therefore, the treatment of such waste water is increasingly gaining attention, and the main treatment methods are chemical methods and biological methods. The application prospect of the biological method is better, especially the anaerobic-aerobic process is the most effective and widely used method for treating the waste water, and the emphasis on how to improve the speed of reducing the dye and the nitrate radical by the microorganism is always on the process.
Researchers find that the redox mediator containing the quinone group can effectively accelerate the biotransformation process of azo dyes, nitrates and the like and improve the degradation rate. The redox mediator containing quinone group has relatively low molecular weight, and may be added directly into water treating system to result in secondary pollution and high continuous feeding cost. The redox mediator containing quinone group is fixed on a water-insoluble physical carrier, so that the method is a feasible industrial method, has the advantage of repeated utilization, is not easy to lose, and avoids secondary pollution.
The invention patent of China granted under the grant publication number CN101862680B discloses a preparation method of a porous inorganic filler fixed quinone compound, which effectively improves the degradation rate of azo dyes. Plating gamma-alumina on the surface of the porous inorganic filler, treating the porous inorganic filler by using 3-amino triethoxysilane to ensure that the surface of the porous inorganic filler contains primary amino, and reacting the primary amino with an anthraquinone compound containing sulfonyl chloride groups to obtain the porous inorganic filler containing quinonyl on the surface. This method has the following problems: (1) the reaction steps are long, the time consumption is long, the final yield is low, and the cost is high; (2) the anthraquinone compound containing sulfonyl chloride group is easy to generate hydrogen chloride gas when contacting water vapor, and the danger is high, so that the production environment is strictly controlled when the anthraquinone compound is used, the operation is inconvenient and the cost is increased; (3) although the porous inorganic filler has a large specific surface area, the internal porous structure is easily blocked by flora and cannot play a role in practical application, and only the quinone-based compound on the surface can play a role in practical application.
The sulfydryl-alkene click chemistry reaction has the characteristics of high efficiency, rapidness, mild reaction conditions, high product yield, simple operation and the like, and is increasingly applied to modification of materials in recent years.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for grafting a redox mediator on the surface of an inorganic filler.
It is another object of the present invention to provide a use of a redox mediator grafted onto the surface of an inorganic filler.
The technical scheme of the invention is as follows:
a method for grafting a redox mediator onto the surface of an inorganic filler, comprising the steps of,
step1, stirring a first organic solvent, a mercaptopropyl silane coupling agent and 0.1wt% of dilute hydrochloric acid at room temperature for 0.5-1 hour, adding the mixture into an inorganic filler, heating to a temperature not higher than 80 ℃, reacting for 1-5 hours, cooling, filtering, washing the filtered solids for 3 times by using absolute ethyl alcohol, and drying to obtain a mercaptopropyl modified inorganic filler;
step2, adding the mercaptopropyl modified inorganic filler obtained in Step1, an allyl-containing redox mediator, a second organic solvent and a photoinitiator into a container, stirring at room temperature, irradiating for 1-30min under ultraviolet light with the dominant wavelength of 365nm and the light intensity of 10-200W/cm, filtering, washing the filtered solids for 3 times by using absolute ethyl alcohol, and drying to obtain the inorganic filler containing the redox mediator.
Preferably, the weight ratio of the first organic solvent, the mercaptopropyl silane coupling agent, the dilute hydrochloric acid and the inorganic filler in Step1 is 1:0.1-0.3:0.01: 0.5-1. The weight ratio of the first organic solvent, the mercaptopropyl silane coupling agent, the dilute hydrochloric acid and the inorganic filler may be 1:0.1:0.01:0.5, 1:0.15:0.01:0.5, 1:0.2:0.01:0.5, 1:0.25:0.01:0.5, 1:0.3:0.01:0.5, 1:0.1:0.01:1, 1:0.15:0.01:1, 1:0.2:0.01:1, 1:0.25:0.01:1 or 1:0.3:0.01:1, but is not limited to the above list.
More preferably, the first organic solvent in Step1 and the second organic solvent in Step2 are selected from one or more of methanol, absolute ethyl alcohol, isopropanol, n-propanol, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone and toluene.
In a further preferred scheme, the first organic solvent in Step1 is selected from one or more of methanol, absolute ethanol, isopropanol and tetrahydrofuran.
In a further preferred scheme, the second organic solvent in Step2 is selected from one or more of tetrahydrofuran, ethyl acetate, butyl acetate and toluene.
More preferably, the mercaptopropyl silane coupling agent in Step1 is one or more selected from the group consisting of 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercaptopropyl-methyldimethoxysilane and 3-mercaptopropyl-methyldiethoxysilane.
More preferably, the average particle size of the inorganic filler in Step1 is 0.1 μm-1 cm, and the inorganic filler is selected from one or more of talcum powder, wollastonite, solid glass microspheres, hollow glass microspheres, heavy calcium carbonate, light calcium carbonate, mica powder, pottery clay, attapulgite and montmorillonite.
The average particle diameter of the inorganic filler may be 1 μm, 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 150 μm, 200 μm, 500 μm, 1mm, but is not limited to the above.
Preferably, the weight ratio of the mercaptopropyl modified inorganic filler, the allyl-containing redox mediator, the second organic solvent and the photoinitiator in Step2 is 1:0.1-0.3:2-10: 0.03-0.06. The weight ratio of the mercaptopropyl-modified inorganic filler, the allyl-containing redox mediator, the second organic solvent, and the photoinitiator may be 1:0.1:3:0.03, 1:0.12:3:0.03, 1:0.15:3:0.03, 1:0.2:3:0.04, 1:0.25:3:0.04, 1:0.3:3:0.06, 1:0.1:5:0.03, 1:0.12:5:0.03, 1:0.15:5:0.03, 1:0.2:5:0.04, 1:0.25:5:0.04, 1:0.3:5:0.06, 1:0.1:8:0.03, 1:0.12:8:0.03, 1:0.15:8:0.03, 1:0.2:8:0.04, 1:0.25: 0.03, 1:8: 0.06, 1: 0.04, 1: 0.06, or more but is not limited thereto.
More preferably, the allyl-containing redox mediator described in Step2 is selected from one or both of 1-allyloxy-4-hydroxyanthraquinone-9, 10-dione and 1-amino-4-allyloxyanthraquinone.
The patent publication No. CN101108795A, the invention granted in China, discloses a method for preparing 1-allyloxy-4-hydroxyanthraquinone-9, 10-dione from 1, 4-dihydroxyanthraquinone-9, 10-dione and propenyl bromide.
Preparation of fluorescence sensor covalently immobilized with 1-amino-4-allyloxyanthraquinone and its application in ornidazole determination, published in "university of Long Sha Liang Li & gt university of sciences (Nature science edition), vol.6, page 77-82", published in 3.2009, reported a method for preparing 1-amino-4-allyloxyanthraquinone using 1-amino-4-hydroxyanthraquinone and bromopropene.
More preferably, the photoinitiator in Step2 is selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, benzophenone, 2, 4-dihydroxy benzophenone, 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (907), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (659), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) and ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate (TPO-L).
An inorganic filler surface-grafted with a redox mediator prepared by the method of any of the preceding claims.
An application of the inorganic filler with the surface grafted with the redox mediator prepared by the method in any scheme in the field of water treatment.
The sulfydryl-alkene click chemistry reaction is a green chemical reaction, has the characteristics of high reaction efficiency, high conversion rate, quick reaction (a plurality of reactions can be completed within minutes or less than one minute), mild reaction conditions (high temperature and high pressure are not needed), high product yield, simple operation and the like, and is increasingly applied to the modification of materials in recent years.
The invention has the beneficial effects that:
(1) the invention adopts inorganic fillers such as talcum powder, wollastonite and solid glass microspheres with low price as physical carriers, has wide sources and low cost;
(2) the method has the advantages of few reaction steps, simple reaction process, no need of heating and pressurizing, and convenient operation;
(3) the invention does not need to adopt raw materials which are easy to contact with moisture to generate toxic and harmful gases;
(4) the inorganic fillers of talcum powder, wollastonite, solid glass microspheres and the like of the grafted redox mediator, which are obtained by the invention, can obviously increase the biodegradation rate of azo dyes and nitrates, and can be continuously used after simple treatment.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Unless otherwise specified, the parts in the following embodiments are parts by weight.
Example 1
100 parts of methanol, 12 parts of 3-mercaptopropyl-trimethoxysilane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1wt% are stirred for 0.5 hour at room temperature, added into 50 parts of 5-micron talcum powder, heated to 50 ℃, reacted for 2 hours, cooled, filtered out solids, washed for 3 times by absolute ethyl alcohol, and dried to obtain the mercaptopropyl-modified talcum powder 1.
100 parts of mercaptopropyl modified talcum powder 1, 10 parts of 1-allyloxy-4-hydroxyanthraquinone-9, 10-dione, 300 parts of tetrahydrofuran and 3 parts of benzoin ethyl ether are added into a container, the mixture is irradiated for 5min under the ultraviolet light with the dominant wavelength of 365nm and the light intensity of 100W/cm under the stirring at room temperature, the filtering is carried out, the solid is filtered out, the washing is carried out for 3 times by using absolute ethyl alcohol, and the drying is carried out, so that the talcum powder 1 grafted with the redox mediator is obtained.
FT-IR analysis showed that the product was 1669cm-1The strong sharp absorption peak is the characteristic absorption peak of carbonyl on anthraquinone structure, and is 1599cm-1A sharp absorption peak with medium intensity is shown as a characteristic absorption peak of the hydrocarbon on the benzene ring, which indicates that the redox mediator is grafted on the surface of the talcum powder. The S element content of the talcum powder before and after fixation is measured by adopting an element analysis method, and the redox mediator content on the surface of the talcum powder 1 is 2.01mmol/g through calculation.
Example 2
100 parts of methanol, 20 parts of 3-mercaptopropyl-trimethoxysilane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1wt% are stirred for 0.5 hour at room temperature, added into 50 parts of 20 mu m talcum powder, heated to 50 ℃, reacted for 2 hours, cooled, filtered out solids, washed for 3 times by absolute ethyl alcohol, and dried to obtain the mercaptopropyl-modified talcum powder 2.
100 parts of mercaptopropyl modified talcum powder 2, 20 parts of 1-allyloxy-4-hydroxyanthraquinone-9, 10-dione, 500 parts of tetrahydrofuran and 4 parts of benzoin dimethyl ether are added into a container, the mixture is irradiated for 25min under the ultraviolet light with the dominant wavelength of 365nm and the light intensity of 20W/cm under the stirring at room temperature, the mixture is filtered, the solid is filtered out and washed for 3 times by absolute ethyl alcohol, and the solid is dried to obtain the talcum powder 2 grafted with the redox mediator.
The content of the S element of the talcum powder before and after grafting is measured by adopting an element analysis method, and the content of the redox mediator on the surface of the talcum powder 2 is 1.78mmol/g through calculation.
Example 3
100 parts of absolute ethyl alcohol, 25 parts of 3-mercaptopropyl triethoxysilane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1wt% are stirred at room temperature for 1 hour, added into 100 parts of wollastonite with the particle size of 100 microns, heated to 70 ℃, reacted for 3 hours, cooled, filtered out solids, washed with absolute ethyl alcohol for 3 times, and dried to obtain mercaptopropyl modified wollastonite 1.
100 parts of mercaptopropyl modified wollastonite 1, 30 parts of 1-allyloxy-4-hydroxyanthraquinone-9, 10-dione, 800 parts of toluene and 6 parts of benzoin dimethyl ether are added into a container, the mixture is irradiated for 5min under the ultraviolet light with the dominant wavelength of 365nm and the light intensity of 150W/cm under the stirring at room temperature, the filtration is carried out, the solid is filtered out and washed for 3 times by absolute ethyl alcohol, and the drying is carried out, so that the wollastonite 1 grafted with the redox mediator is obtained.
The S element content of the wollastonite before and after grafting is measured by an element analysis method, and the redox mediator content of the surface of the wollastonite 1 is 1.52mmol/g through calculation.
Example 4
100 parts of absolute ethyl alcohol, 20 parts of 3-mercaptopropyl triethoxysilane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1wt% are stirred at room temperature for 1 hour, added into 50 parts of wollastonite with the particle size of 500 microns, heated to 70 ℃, reacted for 3 hours, cooled, filtered out solids, washed with absolute ethyl alcohol for 3 times, and dried to obtain mercaptopropyl modified wollastonite 2.
Adding 100 parts of mercaptopropyl modified wollastonite 2, 25 parts of 1-amino-4-allyloxy anthraquinone, 500 parts of toluene and 4 parts of benzoin dimethyl ether into a container, stirring at room temperature, irradiating for 10min under ultraviolet light with the main wavelength of 365nm and the light intensity of 100W/cm, filtering, washing the filtered solids with absolute ethyl alcohol for 3 times, and drying to obtain the wollastonite 2 grafted with the redox mediator.
The S element content of the wollastonite before and after grafting is measured by an element analysis method, and the redox mediator content of the wollastonite 2 surface is 1.27mmol/g through calculation.
Example 5
100 parts of absolute ethyl alcohol, 15 parts of 3-mercaptopropyl triethoxysilane and 1 part of dilute hydrochloric acid with the mass concentration of 0.1wt% are stirred at room temperature for 0.5 hour, added into 50 parts of 100 mu m solid glass microspheres, heated to 70 ℃, reacted for 4 hours, cooled, filtered out solids, washed for 3 times by the absolute ethyl alcohol, and dried to obtain the mercaptopropyl modified solid glass microspheres.
Adding 100 parts of mercaptopropyl modified solid glass microspheres, 25 parts of 1-amino-4-allyloxyanthraquinone, 300 parts of tetrahydrofuran and 4 parts of benzoin dimethyl ether into a container, stirring at room temperature, irradiating for 5min under ultraviolet light with the main wavelength of 365nm and the light intensity of 150W/cm, filtering, washing the filtered solids for 3 times by using absolute ethyl alcohol, and drying to obtain the solid glass microspheres grafted with the redox mediator.
The S element content of the solid glass microspheres before and after fixation is measured by adopting an element analysis method, and the redox mediator content on the surfaces of the solid glass microspheres is 1.42mmol/g through calculation.
Testing
And (3) testing the degradation acceleration effect of the azo dye: after washing 2g of talc blank, 2g of wollastonite blank and 2g of the product of examples 1 to 5, to which a redox mediator was surface-grafted, with physiological saline for 3 times, respectively, 200ml of 120mg/L acid Red B containing an azo dye-degrading strain GYZ (staphylococcus sp.) in the logarithmic phase was added to perform a discoloration test, and the change of the acid Red B concentration with time was measured. The results are shown in Table 1.
Nitrate degradation acceleration effect test: 2g of blank talc, 2g of blank wollastonite, and 2g of the product of examples 1 to 5, to which a redox mediator was surface-grafted, were washed with physiological saline for 3 times, and then added to 200ml of nitrate wastewater containing 150mg/L of denitrifying microorganisms in the logarithmic growth phase for testing, and the change in the nitrate concentration with time was measured. The results are shown in Table 2.
And (3) stability testing: 2g of the inorganic fillers having the anthraquinone compounds surface-grafted in examples 1 to 5 were washed with physiological saline for 3 times, respectively, and then added to 200ml of 120mg/L acid Red B containing an azo dye-degrading strain GYZ (staphylococcus sp.) in the logarithmic growth phase to perform a decolorization test, and the concentration of the acid Red B after 8 hours was measured. The inorganic filler with the surface grafted with the anthraquinone compound after the test is washed and dried by clear water and absolute ethyl alcohol, and then the decolorization test is carried out for 8 hours by using acid red B according to the method, and the test is repeated for 12 times. The results are shown in Table 3.
TABLE 1 acid Red B degradation acceleration test results
As can be seen from Table 1, the inorganic filler with a surface grafted redox mediator of the present invention has a significant effect of promoting the degradation of azo dyes of acid Red B, and the degradation of acid Red B is faster with the increase of the content of the redox mediator. Thus, the inorganic filler with the surface-grafted redox mediator of the present invention can degrade azo dyes more rapidly.
TABLE 2 nitrate degradation acceleration test results
As can be seen from Table 2, the inorganic filler with a surface grafted redox mediator of the present invention has a significant effect of promoting the degradation of nitrate, and the degradation of nitrate is faster as the content of the redox mediator is increased. Thus, the inorganic filler material employing the surface-grafted redox mediator of the present invention is able to degrade nitrates more rapidly.
TABLE 3 degradation stability determination results for acid Red B
As can be seen from Table 3, the inorganic filler with a surface grafted with a redox mediator obtained by the present invention has a good effect after repeated use for 12 times in promoting the biodegradation of azo dyes.
In conclusion, the inorganic filler with the surface grafted with the redox mediator has a good promotion effect on the biodegradation of azo dyes and nitrates, is good in stability, can be repeatedly used, and can be widely applied to water treatment.
The foregoing has shown and described the fundamental principles, major features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A method for grafting a redox mediator onto the surface of an inorganic filler, characterized in that: step1, stirring a first organic solvent, a mercaptopropyl silane coupling agent and 0.1wt% of dilute hydrochloric acid at room temperature for 0.5-1 hour, adding the mixture into an inorganic filler, heating to a temperature not higher than 80 ℃, reacting for 1-5 hours, cooling, filtering out solids, washing the solids for 3 times by using absolute ethyl alcohol, and drying to obtain the mercaptopropyl modified inorganic filler; the first organic solvent is selected from one or more of methanol, absolute ethyl alcohol, isopropanol and n-propanol; the average particle size of the inorganic filler is 0.1-1 cm, and the inorganic filler is selected from one or more of talcum powder, wollastonite, solid glass microspheres, hollow glass microspheres, heavy calcium carbonate, light calcium carbonate, mica powder, argil, attapulgite and montmorillonite;
step2, adding the mercaptopropyl modified inorganic filler obtained in Step1, an allyl-containing redox mediator, a second organic solvent and a photoinitiator into a container, stirring at room temperature, irradiating for 1-30min under ultraviolet light with the dominant wavelength of 365nm and the light intensity of 10-200W/cm, filtering, washing the filtered solids for 3 times by using absolute ethyl alcohol, and drying to obtain the inorganic filler containing the redox mediator; the second organic solvent is selected from one or more of ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone and toluene; the allyl-containing redox mediator is selected from one or two of 1-allyloxy-4-hydroxyanthraquinone-9, 10-dione and 1-amino-4-allyloxyanthraquinone.
2. The method of claim 1, wherein: the weight ratio of the first organic solvent, the mercaptopropyl silane coupling agent, the dilute hydrochloric acid and the inorganic filler in Step1 is 1:0.1-0.3:0.01: 0.5-1.
3. The method according to claim 1 or 2, characterized in that: the mercaptopropyl silane coupling agent in Step1 is one or more selected from 3-mercaptopropyl trimethoxy silane, 3-mercaptopropyl triethoxy silane, 3-mercaptopropyl methyl dimethoxy silane and 3-mercaptopropyl methyl diethoxy silane.
4. The method of claim 1, wherein: the weight ratio of the mercaptopropyl modified inorganic filler, the allyl-containing redox mediator, the second organic solvent and the photoinitiator in Step2 is 1:0.1-0.3:2-10: 0.03-0.06.
5. The method according to claim 1 or 4, characterized in that: the photoinitiator in Step2 is selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, and benzophenone, 2, 4-dihydroxy benzophenone, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and one or more of 2,4, 6-trimethylbenzoyl phenyl phosphonic acid ethyl ester.
6. An inorganic filler surface-grafted with a redox mediator prepared by the method of any one of claims 1 to 5.
7. Use of an inorganic filler having a surface grafted with a redox mediator, prepared by a process according to any one of claims 1 to 5, in the field of water treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910357677.3A CN110040842B (en) | 2019-04-29 | 2019-04-29 | Method for grafting redox mediator on surface of inorganic filler and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910357677.3A CN110040842B (en) | 2019-04-29 | 2019-04-29 | Method for grafting redox mediator on surface of inorganic filler and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110040842A CN110040842A (en) | 2019-07-23 |
| CN110040842B true CN110040842B (en) | 2020-06-16 |
Family
ID=67280235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910357677.3A Active CN110040842B (en) | 2019-04-29 | 2019-04-29 | Method for grafting redox mediator on surface of inorganic filler and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110040842B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028636B (en) * | 2019-04-29 | 2020-04-21 | 厦门理工学院 | Method for preparing anthraquinone compound-containing tourmaline by sulfydryl-alkene click chemistry and application |
| CN111533130A (en) * | 2020-04-23 | 2020-08-14 | 厦门理工学院 | Preparation method of anthraquinone modified MXene two-dimensional layered material, modified microfiltration membrane and application |
| CN111495220A (en) * | 2020-04-23 | 2020-08-07 | 厦门理工学院 | Preparation method of modified MXene two-dimensional layered material, modified microfiltration membrane and application |
| CN111825215B (en) * | 2020-06-17 | 2022-05-10 | 龙岩市厦龙工程技术研究院 | Membrane bioreactor treatment method for nitrogen-containing wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646945A (en) * | 2016-03-30 | 2016-06-08 | 南昌航空大学 | Method for preparing nanometer silicon dioxide grafted carbon fiber reinforcements by aid of mercapto-alkene click reaction |
| CN105696306A (en) * | 2015-11-11 | 2016-06-22 | 陕西科技大学 | Method for preparing super-hydrophobic textile from thiol-ene click chemistry-modified fiber |
| CN105778156A (en) * | 2016-03-27 | 2016-07-20 | 华南理工大学 | Novel rubber compound stuffing preparing method based on mercapto-alkene chemical reaction |
| CN107011534A (en) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | A kind of super-hydrophobic super-oleophylic melamine foamed plastic and preparation method and application |
| CN107699099A (en) * | 2017-10-13 | 2018-02-16 | 浙江大学 | A kind of fluorescent visual type electronic protection coating composition and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5188703A (en) * | 1975-01-27 | 1976-08-03 | KURAFUTOPARUPUJOKAIYAKUHINKAISHUKOTEINIOKERU HAKUEKI JAKUEKI MATAHA RYOKUEKICHUNORYUKANATORIUMUNO SANKAHOHO |
-
2019
- 2019-04-29 CN CN201910357677.3A patent/CN110040842B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696306A (en) * | 2015-11-11 | 2016-06-22 | 陕西科技大学 | Method for preparing super-hydrophobic textile from thiol-ene click chemistry-modified fiber |
| CN105778156A (en) * | 2016-03-27 | 2016-07-20 | 华南理工大学 | Novel rubber compound stuffing preparing method based on mercapto-alkene chemical reaction |
| CN105646945A (en) * | 2016-03-30 | 2016-06-08 | 南昌航空大学 | Method for preparing nanometer silicon dioxide grafted carbon fiber reinforcements by aid of mercapto-alkene click reaction |
| CN107011534A (en) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | A kind of super-hydrophobic super-oleophylic melamine foamed plastic and preparation method and application |
| CN107699099A (en) * | 2017-10-13 | 2018-02-16 | 浙江大学 | A kind of fluorescent visual type electronic protection coating composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110040842A (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110040842B (en) | Method for grafting redox mediator on surface of inorganic filler and application | |
| CN110040843B (en) | Preparation method and application of anthraquinone compound fixed on surface of inorganic filler | |
| CN110040844B (en) | Preparation method and application of anthraquinone compound grafted on surface of inorganic filler | |
| CN110066009B (en) | Tourmaline containing anthraquinone compound, preparation method and application | |
| CN110092389B (en) | Tourmaline with anthraquinone compound grafted on surface, preparation method and application | |
| CN110028636B (en) | Method for preparing anthraquinone compound-containing tourmaline by sulfydryl-alkene click chemistry and application | |
| CN110157031B (en) | Preparation method and application of anthraquinone compound grafted on plastic surface | |
| CN113736095B (en) | Method for degrading and detecting organophosphorus pesticide by using Fe-CDs and MOF-808 composite material | |
| Maniyam et al. | Immobilized cells of Rhodococcus strain UCC 0004 as source of green biocatalyst for decolourization and biodegradation of methyl orange | |
| CN112275321B (en) | Preparation method and application of flexible composite catalytic membrane | |
| CN109336670B (en) | Method for modifying grease and application thereof | |
| CN109999835A (en) | A kind of carbonization bacteria cellulose-cadmium sulfide composite photocatalyst material and its preparation method and application | |
| CN115925131B (en) | Composite carbon source and production process thereof | |
| CN112169774A (en) | Straw-based dye adsorbent and preparation method and application thereof | |
| CN110157007B (en) | Preparation method and application of plastic surface grafted graphene and anthraquinone compound | |
| CN112358059B (en) | Application method of pyrite in sewage treatment | |
| CN113813919A (en) | Preparation method and application of aminated biomass carbon material | |
| CN113426436A (en) | Preparation method of composite material and application of composite material in photocatalytic disinfection in water | |
| CN113683077A (en) | Oil-soluble carbon quantum dot, preparation method thereof and anti-ultraviolet master batch prepared from oil-soluble carbon quantum dot | |
| CN110540985B (en) | Photosynthetic bacterium carbon-loaded three-nitrogen-loaded four-nano material | |
| CN115368624B (en) | Porous hydrogel water-retaining material based on kitchen waste, and preparation method and application thereof | |
| CN107235531B (en) | A kind of purifying agent for polluted water of modifying titanium dioxide chelating poly aluminium iron silicate | |
| CN110575820A (en) | preparation method of agricultural and forestry waste adsorbing material for printing and dyeing wastewater treatment | |
| CN115814834B (en) | Simple modification method for enhancing performance of graphite carbon nitride material through post-treatment of solvent | |
| CN115417723B (en) | Modified composite water-retaining gel slow-release nitrogen fertilizer based on kitchen waste and preparation method thereof |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231208 Address after: 361000 Xixi Village, Tieshan Town, Xinluo District, Longyan City, Fujian Province Patentee after: Longyan Water Development Co.,Ltd. Address before: No. 600, Ligong Road, Jimei District, Xiamen City, Fujian Province 361000 Patentee before: XIAMEN University OF TECHNOLOGY Patentee before: XIAMEN JIARONG TECHNOLOGY Corp.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: Room 1002, Building L, No. 38 Tianping Road, Xinluo District, Longyan City, Fujian Province, 364000 Patentee after: Longyan Shuifa Environmental Group Co.,Ltd. Country or region after: China Address before: 361000 Xixi Village, Tieshan Town, Xinluo District, Longyan City, Fujian Province Patentee before: Longyan Water Development Co.,Ltd. Country or region before: China |