CN111036297A - Carbon fiber modified based on iron alginate, preparation method and application - Google Patents
Carbon fiber modified based on iron alginate, preparation method and application Download PDFInfo
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- CN111036297A CN111036297A CN201911296624.1A CN201911296624A CN111036297A CN 111036297 A CN111036297 A CN 111036297A CN 201911296624 A CN201911296624 A CN 201911296624A CN 111036297 A CN111036297 A CN 111036297A
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- carbon fiber
- alginate
- iron
- solution
- dye
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 75
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 75
- 229940072056 alginate Drugs 0.000 title claims abstract description 74
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 70
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 52
- 239000002351 wastewater Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 23
- 235000010413 sodium alginate Nutrition 0.000 claims description 18
- 239000000661 sodium alginate Substances 0.000 claims description 18
- 229940005550 sodium alginate Drugs 0.000 claims description 18
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 14
- 239000002957 persistent organic pollutant Substances 0.000 claims description 12
- 229920000297 Rayon Polymers 0.000 claims description 10
- -1 alginate modified carbon fiber Chemical class 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000000987 azo dye Substances 0.000 claims description 3
- 235000010410 calcium alginate Nutrition 0.000 claims description 3
- 239000000648 calcium alginate Substances 0.000 claims description 3
- 229960002681 calcium alginate Drugs 0.000 claims description 3
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 239000000980 acid dye Substances 0.000 claims description 2
- 239000000981 basic dye Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000000982 direct dye Substances 0.000 claims description 2
- 239000000986 disperse dye Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 235000001055 magnesium Nutrition 0.000 claims description 2
- 229940091250 magnesium supplement Drugs 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 235000010408 potassium alginate Nutrition 0.000 claims description 2
- 239000000737 potassium alginate Substances 0.000 claims description 2
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 2
- 239000000985 reactive dye Substances 0.000 claims description 2
- 239000000988 sulfur dye Substances 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 27
- 238000007639 printing Methods 0.000 abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000006978 adaptation Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 239000010802 sludge Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract 2
- 229910021641 deionized water Inorganic materials 0.000 abstract 2
- 229960001126 alginic acid Drugs 0.000 abstract 1
- 239000000783 alginic acid Substances 0.000 abstract 1
- 150000004781 alginic acids Chemical class 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 14
- WXLFIFHRGFOVCD-UHFFFAOYSA-L azophloxine Chemical compound [Na+].[Na+].OC1=C2C(NC(=O)C)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 WXLFIFHRGFOVCD-UHFFFAOYSA-L 0.000 description 12
- 235000012739 red 2G Nutrition 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- XWZDJOJCYUSIEY-UHFFFAOYSA-L disodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O XWZDJOJCYUSIEY-UHFFFAOYSA-L 0.000 description 3
- 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 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 3
- 230000002085 persistent effect Effects 0.000 description 3
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 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 1
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940052223 basic fuchsin Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- BUFQZEHPOKLSTP-UHFFFAOYSA-M sodium;oxido hydrogen sulfate Chemical compound [Na+].OS(=O)(=O)O[O-] BUFQZEHPOKLSTP-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000003911 water pollution 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a carbon fiber modified based on ferric alginate, a preparation method and application thereof. The preparation method comprises the following steps: (1) carrying out acid washing and drying pretreatment on the carbon fiber; (2) dissolving ferric salt in deionized water to obtain a ferric salt solution; (3) dissolving alginate in deionized water to obtain an alginate solution; (4) mixing the ferric salt solution and the alginic acid solution according to the proportion and stirring uniformly; (5) loading the iron alginate solution on the carbon fiber by using an impregnation method; (6) and taking out the carbon fiber, draining residual solution on the surface, and drying the carbon fiber in an oven to obtain the modified carbon fiber based on the ferric alginate. The invention has simple manufacture and lower requirement on reaction, can activate the oxidant to generate the active oxidation species under the condition of pH 2-10 to efficiently degrade the printing and dyeing wastewater, can be repeatedly used for more than 7 times, overcomes the problems of narrow pH adaptation range, easy generation of iron sludge and the like of the traditional Fenton technology and the current Fenton-like technology, has more obvious removal effect and higher wastewater degradation efficiency.
Description
Technical Field
The invention belongs to the technical field of printing and dyeing wastewater organic matter treatment, and particularly relates to a preparation method and application of modified carbon fiber based on ferric alginate.
Background
The textile industry plays an important role in national economy as a strut-type traditional enterprise in national economy, but the amount of industrial wastewater generated by the printing and dyeing industry, a midstream industry, is extremely large. A large amount of untreated printing and dyeing wastewater is discharged into the environment to cause direct or indirect influence on human health and ecological environment, and the treatment of printing and dyeing industrial wastewater becomes a great obstacle for realizing green, environmental and economic performances in China. Therefore, the development of a new efficient and environment-friendly wastewater treatment method has great practical significance.
Among the various water pollution control methods, fenton oxidation technology is a typical advanced oxidation technology, and is widely favored by researchers due to its advantages of high efficiency, environmental protection, recycling, etc., but there are still some problems that limit its application, such as: (1) a large amount of ferrous ions and ferric ions in the reaction system easily form iron sludge which is difficult to treat along with the reaction, increase COD in the wastewater and cause secondary pollution; (2) the pH adaptation range of the reaction is too narrow, and the reaction can only play a role under the strong acid condition that the pH value is 2-3.5; (3) it is difficult to degrade certain organic matters with special structures, such as perfluorocarboxylic acid and the like.
In order to solve the problems of the Fenton method, recently, light, sound and electrocatalysis are applied to a catalyst system, and other transition metal ions are considered to be used instead of Fe2+Chinese patent CN 108452820A, "a carbon nitride/α type iron oxide catalyst, a photoelectric auxiliary Fenton-like system and application thereof in organic wastewater treatment" discloses a carbon nitride/α type iron oxide heterojunction catalyst, and combines the catalyst with visible light, low-voltage bioelectricity and persulfateChinese patent No. 106362746B discloses a magnetic fenton-like catalyst, a preparation method and an application thereof, the catalyst can be effectively separated under an external magnetic field, the problem of difficulty in catalyst recovery is solved, the catalyst has stable properties and excellent catalytic activity in the fenton reaction, has a wide pH adaptation range and can be widely applied to organic wastewater treatment, and chinese patent No. CN 106552627B discloses a preparation method and an application thereof based on copper oxide modified carbon fiber, the catalyst has good catalytic activity, can activate an oxidizing agent to generate an oxygen active carbon fiber under the condition of pH 3-10 to efficiently degrade wastewater, the problem of low energy consumption and high efficiency of the catalyst preparation are solved, and the wastewater treatment is not suitable for a printing and dyeing wastewater treatment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the carbon fiber based on the modification of the ferric alginate, which has the advantages of high efficiency in wastewater treatment, convenient preparation, environmental protection, mild reaction condition and low use cost, and the preparation method and the application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of carbon fiber based on modification of iron alginate comprises the following steps:
1) carrying out acid washing and drying pretreatment on the carbon fiber;
2) dissolving ferric salt into ferric salt solution with the molar concentration of 0.04-0.5 mol/L;
3) dissolving alginate into alginate solution with molar concentration of 0.04-0.5mol/L, and stirring to dissolve completely;
4) mixing an iron salt solution and an alginate solution according to the mass ratio of solute of 1 (0.5-10) and uniformly stirring to obtain an iron alginate solution;
5) and (3) dipping the pretreated carbon fiber in an iron alginate solution for 1-24h, taking out the activated carbon fiber, washing and drying to obtain the activated carbon fiber modified based on the iron alginate.
The invention uses the dipping method to load the copper salt on the carbon fiber, which is beneficial to keeping the activity of the iron alginate, and can greatly reduce the preparation process, not only improve the catalytic activity of the catalyst, but also have simple and controllable preparation, and achieve the effect of efficiently degrading pollutants.
Further, said iron salt and said iron salt comprise FeCl2、FeCl3、Fe(NO3)3、FeSO4、Fe2(SO4)3One or more of (a).
Further, the alginate comprises sodium alginate, potassium alginate, calcium alginate or magnesium alginate.
Further, the carbon fiber includes activated carbon fiber, polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, viscose-based carbon fiber, phenol-formaldehyde-based carbon fiber, or vapor-grown carbon fiber.
Further, the method for pretreating the carbon fiber comprises the following steps: mixing carbon fiber with 1-5mol/L nitric acid, reacting at 30-70 deg.C for 1-6 hr, washing, and oven drying at 30-70 deg.C.
The invention also aims to provide the carbon fiber based on the modification of the ferric alginate prepared by the preparation method.
The invention also aims to provide an application of the carbon fiber based on the modification of the iron alginate, which specifically comprises the following steps: it is used for degrading organic pollutants of dyes.
Further, the specific degradation method comprises the following steps: adding 0.1-50g/L of wastewater based on ferric alginate modified carbon fiber and 0.01-100mmol/L of wastewater oxidant into dye wastewater with the concentration of 0.01-0.5g/L and the pH value of 2-10; then placing the reaction system in an environment irradiated by visible light, and reacting for 5-60min at 10-80 ℃; the oxidant is one or the combination of two of hydrogen peroxide and persulfate.
Further, the dosage of the modified carbon fiber based on the ferric alginate is 1-20g/L of wastewater; the adding concentration of the oxidant is 0.1-50mmol/L wastewater. The catalyst can efficiently degrade the printing and dyeing wastewater under the dosage; the concentration of the oxidant is in the range, and the printing and dyeing wastewater can be efficiently degraded.
Further, the dye organic pollutant comprises one or two of reactive dye, acid dye, basic dye, disperse dye, azo dye, sulfur dye and direct dye.
The invention has convenient preparation and low requirement on reaction, and can quickly activate the oxidant to generate active oxidation species (sulfate radical free radical SO) under the condition of pH 2-104 -OH) can be reused for more than 7 times, overcomes the defects of narrow pH application range, easy generation of iron sludge and the like of the traditional Fenton technology, and has great implementation value and social and economic benefits.
The method overcomes the defects of low oxidant utilization rate, narrow pH application range and the like in the traditional Fenton technology, can effectively inhibit potential secondary pollution of intermediate products in the catalytic degradation process, and can efficiently treat the organic printing and dyeing wastewater. Compared with the prior art, the invention has the following advantages: (1) the PMS is efficiently activated to degrade the printing and dyeing wastewater, and the azo dye is completely degraded within 24 minutes; (2) the pH adaptation range is wide (2-10), and the pH adaptation agent can be repeatedly used for more than 7 times; (3) can be directly used under visible light; (4) the catalyst is simple to prepare, green and environment-friendly, has mild reaction conditions, does not need external energy input, is convenient to operate and has low cost.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the iron alginate-based modified carbon fiber prepared by the example;
FIG. 2 is a schematic diagram of dye degradation under visible light irradiation based on iron alginate modified carbon fiber in combination with an oxidizing agent prepared in example 1;
FIG. 3 is a graph showing the effect of activated oxidants based on iron alginate modified carbon fibers prepared in example 1 on acid Red 1 dye removal;
FIG. 4 is a graph (%) showing the effect of removing various kinds of dyes from the iron alginate-based modified carbon fiber prepared in example 1;
FIG. 5 is a graph of the dye removal effect of the carbon fiber based on iron alginate modification prepared in example 6 at different pH values;
fig. 6 is a schematic representation of the reusability of iron alginate-based modified carbon fibers prepared in example 7.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
0.1g of sodium alginate is dissolved in 200mL of distilled water and stirred uniformly. 0.1g of ferric chloride is dissolved in 100mL of distilled water and stirred until dissolved. Pouring the ferric chloride solution into the sodium alginate solution, and stirring to be gelatinous to obtain the ferric alginate solution. Mixing activated carbon fibers with nitric acid, reacting for 6 hours at 30 ℃ after the concentration of the nitric acid is 3mol/L, washing and drying at 40 ℃. After the activated carbon fiber is subjected to the acidification pretreatment, 0.1g of the activated carbon fiber is cut into pieces with the length and the width of about 1cm and added into an iron alginate solution, the mixed solution is kept stand at 30 ℃ for 24 hours, the activated carbon fiber is taken out, the residual solution is drained, and the activated carbon fiber is placed in a 30 ℃ drying oven for 12 hours, so that the carbon fiber based on the modification of the iron alginate and having the characteristic of efficiently treating the organic printing and dyeing wastewater is obtained, and the process diagram is shown in figure 1.
The schematic diagram of the iron alginate-based modified carbon fiber synergistic oxidant prepared in the example for degrading the dye under the irradiation of visible light is shown in fig. 2, which showsCan quickly activate oxidant under illumination to generate active oxide species (sulfate radical SO)4 -And hydroxyl radical OH), and further efficiently degrading organic pollutants in the printing and dyeing wastewater.
The iron alginate modified fiber prepared in this example was used for the following degradation reaction test of organic pollutants:
the reaction was carried out in a 50ml reaction vessel, and after 0.1g of activated carbon fiber and 0.5mM of potassium hydrogen peroxymonosulfate were added to 30ml of printing and dyeing wastewater (acid red 1 having a pH of 6 and a concentration of 50. mu.M) in succession and reacted at 30 ℃ for 24min, the dye acid red 1 was removed 100%, and the effect graph is shown in FIG. 3. In the embodiment, the activated carbon fiber and the potassium monopersulfate form a catalytic oxidation system based on persistent free radicals, the activated carbon fiber of the catalytic oxidation system can provide the persistent free radicals, so that the catalytic oxidation system has the advantage of long service life, and the persistent free radicals can also serve as electron donors to provide free electrons to accelerate the oxidation-reduction reaction process important in environmental catalysis.
In addition, in order to test the removal effect of the carbon fiber modified by the ferric alginate on different dyes, the carbon fiber is further used for carrying out removal tests on acid orange, acid red 1, rhodamine B, reactive brilliant red X-3B, methylene blue, basic green 4 and basic fuchsin. The results are shown in fig. 4, which shows that the carbon fiber has an extremely high removal rate for different dyes.
Example 2
0.1g of magnesium alginate is dissolved in 200mL of distilled water and is uniformly stirred. 0.1g of ferric nitrate was dissolved in 100mL of distilled water, and the solution was stirred until dissolved. Pouring the ferric nitrate solution into the magnesium alginate solution and stirring the mixture to be gelatinous to obtain the ferric alginate solution. Mixing the viscose-based carbon fiber with nitric acid, reacting for 5 hours at 70 ℃ after the nitric acid concentration is 1mol/L, and drying at 60 ℃ after washing. After acidizing pretreatment, 0.05g of viscose-based carbon fiber is cut into pieces with the length and the width of about 1cm and added into an iron alginate solution, the mixed solution is kept stand at 35 ℃ for 24 hours, the viscose-based carbon fiber is taken out, the residual solution is drained, and the viscose-based carbon fiber is placed in a 30 ℃ drying oven for 12 hours, so that the carbon fiber based on the modification of the iron alginate and having the characteristic of efficiently treating the organic printing and dyeing wastewater is obtained.
The iron alginate modified fiber prepared in this example was used for the following degradation reaction test of organic pollutants:
the reaction was carried out in a 50ml reaction vessel, and 0.05g of activated carbon fiber was placed in 30ml of printing and dyeing wastewater (methylene blue with a pH of 4 and a concentration of 50. mu.M) in succession with 0.5mM sodium hydrogen peroxymonosulfate, and after reaction at 30 ℃ for 20min, the dye methylene blue was removed to 99%.
Example 3
0.2g of sodium alginate is dissolved in 200mL of distilled water and stirred uniformly. 0.1g of ferric chloride is dissolved in 100mL of distilled water and stirred until dissolved. Pouring the ferric chloride solution into the sodium alginate solution and stirring the solution to be gelatinous to obtain the ferric alginate solution. Mixing the viscose-based carbon fiber with nitric acid, reacting for 7 hours at 40 ℃ after the nitric acid concentration is 5mol/L, washing and drying at 50 ℃. And then adding 0.1g of viscose-based carbon fiber which is cut into pieces and has the length and the width of about 1cm into a sodium alginate solution, standing the mixed solution at 30 ℃ for reaction for 24 hours, taking out the viscose-based carbon fiber, draining the residual solution, and placing the viscose-based carbon fiber in an oven at 30 ℃ for 12 hours to obtain the carbon fiber based on the modification of the iron alginate, which has the characteristic of efficiently treating the organic printing and dyeing wastewater.
The iron alginate modified fiber prepared in this example was used for the following degradation reaction test of organic pollutants:
the reaction was carried out in a 50ml reaction vessel, and after 0.1g of activated carbon fiber and 0.5mM of sodium persulfate were put in succession into 30ml of printing and dyeing wastewater (50. mu.M reactive Brilliant Red X-3B with pH 6) and reacted at 30 ℃ for 24min, 98% of the dye reactive Brilliant Red X-3B was removed.
Example 4
0.2g of sodium alginate is dissolved in 200mL of distilled water and stirred uniformly. 0.1g of ferric chloride is dissolved in 100mL of distilled water and stirred until dissolved. Pouring the ferric chloride solution into the sodium alginate solution and stirring the solution to be gelatinous to obtain the ferric alginate solution. Mixing polyacrylonitrile-based carbon fibers with nitric acid, reacting for 6 hours at 30 ℃ after the nitric acid concentration is 3mol/L, and drying at 40 ℃ after washing. And then adding 0.2g of polyacrylonitrile-based carbon fiber which is cut into pieces and has the length and the width of about 1cm into a sodium alginate aqueous solution, standing the mixed solution at 40 ℃ for 24 hours, placing the mixed solution in a 50 ℃ oven for 12 hours, taking out the carbon fiber, and draining the residual solution to obtain the sodium alginate modified carbon fiber with the characteristic of efficiently treating the organic printing and dyeing wastewater.
The iron alginate modified fiber prepared in this example was used for the following degradation reaction test of organic pollutants:
the reaction was carried out in a 50ml reaction vessel, and after 0.2g of modified carbon fiber and 0.5mM potassium hydrogen Peroxymonosulfate (PMS) were added successively to 30ml of printing and dyeing wastewater (acid red (AR1) having a pH of 10 and a concentration of 50. mu.M) and reacted at 30 ℃ for 24min, the removal rate of dye AR1 was 99% or more.
Example 5
1g of sodium alginate is taken and dissolved in 200mL of distilled water, and the mixture is uniformly stirred. 0.1g of ferric chloride is dissolved in 100mL of distilled water and stirred until dissolved. Pouring the ferric chloride solution into the sodium alginate solution and stirring the solution to be gelatinous to obtain the ferric alginate solution. Mixing phenolic carbon fiber with nitric acid, reacting at 50 ℃ for 5 hours with the concentration of the nitric acid being 2mol/L, washing and drying at 50 ℃. And then adding 0.2g of phenolic aldehyde carbon fiber which is cut into pieces and has the length and the width of about 1cm into the sodium alginate aqueous solution, standing the mixed solution at 50 ℃ for reaction for 24 hours, taking out the carbon fiber, draining the residual solution, and placing the carbon fiber in an oven at 55 ℃ for 12 hours to obtain the carbon fiber based on sodium alginate modification and having the characteristic of efficiently treating the organic printing and dyeing wastewater.
The iron alginate modified fiber prepared in this example was used for the following degradation reaction test of organic pollutants:
the reaction was carried out in a 50ml reaction vessel, and after 0.2g of modified carbon fiber and 1mM hydrogen peroxide were sequentially added to 30ml of printing and dyeing wastewater (acid red 1 at a concentration of 50 μ M and pH 4) and reacted at 30 ℃ for 24min, the removal rate of dye acid red 1 reached 99% or more.
Example 6
0.2g of sodium alginate is dissolved in 200mL of distilled water and stirred uniformly. 0.1g of ferric chloride is dissolved in 100mL of distilled water and stirred until dissolved. Pouring the ferric chloride solution into the sodium alginate solution, and stirring to be gelatinous to obtain the ferric alginate solution. Mixing activated carbon fibers with nitric acid, reacting for 6 hours at 30 ℃ after the concentration of the nitric acid is 3mol/L, washing and drying at 40 ℃. After the activated carbon fiber is subjected to acidification pretreatment, 0.1g of the activated carbon fiber is cut into pieces with the length and the width of about 1cm and added into an iron alginate solution, the mixed solution is kept stand at 30 ℃ for reaction for 24 hours, the activated carbon fiber is taken out, the residual solution is drained, and the activated carbon fiber is placed in a 30 ℃ oven for 12 hours, so that the carbon fiber based on the modification of the iron alginate and having the characteristic of efficiently treating the organic printing and dyeing wastewater is obtained, and the process diagram is shown in figure 1.
The iron alginate modified fiber prepared in this example was used for the following degradation reaction test of organic pollutants:
the reaction was carried out in a 50ml reaction vessel, 0.1g of activated carbon fibers and 0.5mM potassium monopersulfate were added successively to 30ml of printing and dyeing wastewater, which in the different treatments were in the following order: the dye acid red 1 was removed 100% after each treatment for 24min at 30 ℃ in acid red 1 with pH of 2, 3, 4, …,10 and concentration of 50. mu.M, and the effect graph is shown in FIG. 5. Therefore, the carbon fiber modified based on the ferric alginate has low requirements on reaction pH, and can efficiently degrade the dye acid red 1 in the printing and dyeing wastewater within a wide pH range of 2-10.
Example 7
0.1g of calcium alginate is dissolved in 200mL of distilled water and is uniformly stirred. 0.2g of ferric chloride was dissolved in 100mL of distilled water, and stirred until dissolved. Pouring the ferric chloride solution into the sodium alginate solution and stirring the solution to be gelatinous to obtain the ferric alginate solution. Mixing activated carbon fibers with nitric acid, reacting for 6 hours at 30 ℃ after the concentration of the nitric acid is 3mol/L, washing and drying at 40 ℃. After the activated carbon fiber is subjected to acidification pretreatment, 0.1g of the activated carbon fiber is cut into pieces with the length and the width of about 1cm and added into an iron alginate solution, the mixed solution is kept stand at 30 ℃ for reaction for 24 hours, the activated carbon fiber is taken out, the residual solution is drained, and the activated carbon fiber is placed in a 30 ℃ oven for 12 hours, so that the carbon fiber based on the modification of the iron alginate and having the characteristic of efficiently treating the organic printing and dyeing wastewater is obtained.
The iron alginate modified fiber prepared in this example was used for the following degradation reaction test of organic pollutants:
the reaction was carried out in a 50ml reaction vessel, and 30ml of the printing and dyeing wastewater was taken, and 0.1g of activated carbon fiber and 0.5mM potassium hydrogen Peroxymonosulfate (PMS) were put in succession into acid Red 1 having a pH of 6 and a concentration of 50. mu.M, and after reaction at 30 ℃ for 24min, the dye acid Red 1 was removed 100%. The used catalyst was taken out and put into 30ml of printing and dyeing wastewater with 0.5mM hydrogen peroxymonosulfate to repeat the first experiment, and after 24min reaction at 30 ℃, the dye acid red 1 was removed 100%. The catalyst was taken out for repeated use, and when the reaction proceeded for the 6 th time, the catalyst still had a high removal rate of the dye, and the effect graph is shown in fig. 6.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.
Claims (10)
1. A preparation method of carbon fiber modified based on ferric alginate is characterized by comprising the following steps:
1) carrying out acid washing and drying pretreatment on the carbon fiber;
2) dissolving ferric salt into ferric salt solution with the molar concentration of 0.04-0.5 mol/L;
3) dissolving alginate into alginate solution with molar concentration of 0.04-0.5mol/L, and stirring to dissolve completely;
4) mixing an iron salt solution and an alginate solution according to the mass ratio of solute of 1 (0.5-10) and uniformly stirring to obtain an iron alginate solution;
5) and (3) dipping the pretreated carbon fiber in an iron alginate solution for 1-24h, taking out the activated carbon fiber, washing and drying to obtain the activated carbon fiber modified based on the iron alginate.
2. The preparation method of carbon fiber based on modification of iron alginate according to claim 1, characterized in that: said iron salt comprising FeCl2、FeCl3、Fe(NO3)3、FeSO4、Fe2(SO4)3One or more of (a).
3. The preparation method of carbon fiber based on modification of iron alginate according to claim 1, characterized in that: the alginate comprises sodium alginate, potassium alginate, calcium alginate or magnesium alginate.
4. The preparation method of carbon fiber based on modification of iron alginate according to claim 1, characterized in that: the carbon fiber comprises activated carbon fiber, polyacrylonitrile-based carbon fiber, asphalt-based carbon fiber, viscose-based carbon fiber, phenolic-based carbon fiber or vapor-grown carbon fiber.
5. The preparation method of carbon fiber based on modification of iron alginate according to claim 1, characterized in that: the method for pretreating the carbon fiber comprises the following steps: mixing carbon fiber with 1-5mol/L nitric acid, reacting at 30-70 deg.C for 1-6 hr, washing, and oven drying at 30-70 deg.C.
6. An iron alginate modified-based carbon fiber prepared according to the preparation method of claim 1.
7. The use of carbon fibers based on modification of iron alginate according to claim 6, characterized in that: it is used for degrading organic pollutants of dyes.
8. Use according to claim 7, characterized in that: adding 0.1-50g/L of wastewater based on ferric alginate modified carbon fiber and 0.01-100mmol/L of wastewater oxidant into dye wastewater with the concentration of 0.01-0.5g/L and the pH value of 2-10; then placing the reaction system in an environment irradiated by visible light, and reacting for 5-60min at 10-80 ℃; the oxidant is one or the combination of two of hydrogen peroxide and persulfate.
9. Use according to claim 8, characterized in that: the dosage of the modified carbon fiber based on the ferric alginate is 1-20g/L of wastewater; the adding concentration of the oxidant is 0.1-50mmol/L wastewater.
10. Use according to any one of claims 7 to 9, wherein: the dye organic pollutant comprises one or two of reactive dye, acid dye, basic dye, disperse dye, azo dye, sulfur dye and direct dye.
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