CN112709068A - Composite material for petrochemical wastewater treatment and preparation method thereof - Google Patents
Composite material for petrochemical wastewater treatment and preparation method thereof Download PDFInfo
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- CN112709068A CN112709068A CN202011592210.6A CN202011592210A CN112709068A CN 112709068 A CN112709068 A CN 112709068A CN 202011592210 A CN202011592210 A CN 202011592210A CN 112709068 A CN112709068 A CN 112709068A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 27
- 239000010881 fly ash Substances 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 238000009987 spinning Methods 0.000 claims abstract description 66
- 239000000243 solution Substances 0.000 claims abstract description 63
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 59
- 239000000835 fiber Substances 0.000 claims abstract description 58
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 32
- NIJWSVFNELSKMF-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=C(F)C(F)=C(F)C(F)=C1F NIJWSVFNELSKMF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004381 surface treatment Methods 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 238000007598 dipping method Methods 0.000 claims abstract description 21
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 19
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 19
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims abstract description 17
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960000583 acetic acid Drugs 0.000 claims abstract description 16
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000012805 post-processing Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 72
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 37
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 238000005229 chemical vapour deposition Methods 0.000 claims description 19
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 8
- 230000015271 coagulation Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 36
- 239000007788 liquid Substances 0.000 description 35
- 238000005470 impregnation Methods 0.000 description 32
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 18
- 239000002351 wastewater Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 230000001112 coagulating effect Effects 0.000 description 15
- 230000005389 magnetism Effects 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000006249 magnetic particle Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012719 thermal polymerization Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- -1 ethylene, propylene, butadiene Chemical class 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/236—Esters of carboxylic acids; Esters of carbonic acid containing halogen atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种石油化工废水处理用复合材料及其制备方法，先将磁性飞灰利用N‑苯氨基甲基三乙氧基硅烷进行改性处理，得到改性磁性飞灰；然后以丙烯腈、衣康酸、甲基丙烯酸甲酯为原料进行聚合反应，并在反应过程中加入改性磁性飞灰，得到纺丝液，纺丝得到纤维；再将N‑苯氨基甲基三乙氧基硅烷、八甲基环四硅氧烷与氢氧化钾水溶液进行第一次反应，接着加入冰醋酸进行第二次反应，然后加入2‑吡啶甲醛进行第三次反应，后处理制成浸渍液；最后将纤维置于浸渍液中进行浸渍处理，并通过全氟苯基甲基丙烯酸酯表面聚合实现表面处理即得。该复合材料具有较好的疏水性，适用于石油化工废水处理，具有良好的处理效果。The invention discloses a composite material for petrochemical wastewater treatment and a preparation method thereof. First, magnetic fly ash is modified with N-anilinomethyltriethoxysilane to obtain modified magnetic fly ash; Nitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, and modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning; then N-anilinomethyl triethoxy Silane, octamethylcyclotetrasiloxane and potassium hydroxide aqueous solution are reacted for the first time, then glacial acetic acid is added for the second reaction, then 2-pyridine aldehyde is added for the third reaction, and the post-processing is used to make a dipping solution ; Finally, the fiber is placed in the dipping solution for dipping treatment, and the surface treatment is realized by the surface polymerization of perfluorophenyl methacrylate. The composite material has good hydrophobicity, is suitable for petrochemical wastewater treatment, and has good treatment effect.
Description
Technical Field
The invention relates to the technical field of preparation of wastewater treatment materials, in particular to a composite material for petrochemical wastewater treatment and a preparation method thereof.
Background
Petrochemical industry refers specifically to the processing industry for producing petroleum products and petrochemical products from petroleum and natural gas. The first step in the production of petrochemical products is the cracking of raw oil and gas (such as propane, gasoline, diesel, etc.) to produce basic chemical materials, typically ethylene, propylene, butadiene, benzene, toluene, xylene. The second step is to produce various organic chemical materials (about 200 kinds) and synthetic materials (plastics, synthetic fibers, synthetic rubbers) from basic chemical materials.
The petrochemical industry is an important industry in China, the production capacity is large, and the production process is relatively complex, so that more waste water is produced in the production process, and the change range of the waste water yield is wide due to different production processes. The waste water discharged in the refining processes of cracking, refining, fractionating and synthesizing petroleum contains various toxic organic pollutants, such as benzopyrene, benzanthracene and other polycyclic aromatic hydrocarbon substances, which have carcinogenic, teratogenic or mutagenic effects, and also contains pollutants such as benzene, phenol, sulfur compounds, gasoline, crude oil and the like. The petrochemical wastewater has large discharge amount and high concentration of suspended matters, contains a large amount of soluble salts, various chemical additives, petroleum and the like, has great influence on soil structure without treatment and discharge, and is harmful to plant growth, wherein heavy metal ions, organic polymers which are not easy to degrade and the like enter a food chain through animals and plants and also can be harmful to human health and life safety.
Once entering water, petrochemical wastewater can immediately diffuse on the water surface to form an oil film, so that the water is prevented from reoxygenating from the atmosphere, dissolved oxygen in the water is reduced, and the petrochemical wastewater is adhered to the surface of aquatic organisms and a respiratory system to cause death; after being ingested, the fish can cause poisoning, influence growth, have peculiar smell and cannot eat; pollutants deposited at the bottom of water are decomposed anaerobically to generate poisons such as hydrogen sulfide and the like, heavy oil products can be adhered to silt, inhabitation, reproduction and other activities of aquatic organisms can be influenced, the growth of the aquatic organisms is seriously influenced, and finally the ecological environment and the human health are influenced.
The existing flocculating agent for treating petrochemical wastewater has unsatisfactory treatment effect and is difficult to realize high-efficiency oil removal, so that the development of a novel high-efficiency flocculating agent suitable for petrochemical wastewater is very necessary.
Patent application CN111268776A discloses a flocculant for petrochemical wastewater treatment and a preparation method thereof, wherein the flocculant is prepared from cationic starch flocculant, zeolite mineral, polymeric ferric sulfate, polymeric aluminum chloride, chitosan derivative, bentonite, alum, water and other raw materials, and the working principle of the flocculant is that oil, emulsified oil and the like in sewage are destabilized and adsorbed on a flocculating constituent, and finally flocculation and sedimentation are realized. However, the petrochemical wastewater has high oil content, and the flocculant has poor hydrophobicity, so that the contact area of the flocculant and the wastewater is limited, and the flocculation effect is seriously influenced.
Disclosure of Invention
The invention aims to provide a composite material for petrochemical wastewater treatment and a preparation method thereof, which have good hydrophobicity and good treatment effect on petrochemical wastewater.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:
(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;
(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;
(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;
(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.
Preferably, the specific method of the step (1) comprises the following steps in parts by weight: adding 1 part of N-phenylaminomethyltriethoxysilane into 3-4 parts of absolute ethyl alcohol, uniformly oscillating by ultrasonic waves, adding 0.5-0.7 part of magnetic fly ash, heating to reflux, stirring for 2-3 hours under heat preservation, and centrifuging to obtain precipitate, thus obtaining the modified magnetic fly ash.
Preferably, in step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of magnet is 10000 ~ 20000 Oe during initial election, the magnet is permanent magnet or electro-magnet.
Preferably, in the step (2), the preparation method of the spinning solution comprises the following steps: adding 100 parts of acrylonitrile, 0.8-1.2 parts of itaconic acid and 8-10 parts of methyl methacrylate into a polymerization kettle, adding 2-3 parts of azobisisobutyronitrile and 450-500 parts of dimethyl sulfoxide, carrying out polymerization reaction for 4-6 hours at 45-55 ℃, adding 10-15 parts of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 5-7 hours to obtain the spinning solution.
Further preferably, the monomer removal and bubble removal treatment is carried out after the polymerization reaction is finished, and the specific method comprises the following steps: treating for 20-30 minutes under the condition of 4-5 kPa.
Preferably, in the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.
Preferably, the spinning solution is metered by a metering pump and extruded by a spinneret with the aperture of 0.05-0.08 mm to form a trickle, and the thickness of the air layer is 22-25 mm.
Preferably, the solidification solution is a dimethyl sulfoxide aqueous solution with the mass concentration of 6-8%; the temperature of the coagulating bath is 30-35 ℃.
Preferably, in the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane, potassium hydroxide aqueous solution, glacial acetic acid and 2-pyridinecarbaldehyde is 1: 3-3.5: 0.3-0.4: 0.6-0.8: 1.8-2.2; the mass concentration of the potassium hydroxide aqueous solution is 30-40%.
Preferably, in the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 4-6 hours at 80-85 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 20-30 minutes at 50-60 ℃; the process conditions of the third reaction are as follows: stirring and reacting for 20-22 hours at 70-80 ℃.
Preferably, in the step (3), the post-treatment method comprises the following specific steps: and (3) evaporating under reduced pressure to obtain an oily substance, adding the oily substance into tetrahydrofuran with the weight 5-7 times that of the oily substance, stirring and dissolving, and filtering insoluble substances to obtain the impregnation liquid.
Preferably, in the step (4), the process conditions of the dipping treatment are as follows in parts by weight: and adding 1 part of fiber into 5-7 parts of impregnation liquid, standing and impregnating for 3-4 hours, and taking out and naturally drying.
Preferably, in the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.
Preferably, the fiber is placed on a sample table at the bottom of the chemical vapor deposition chamber, a heating wire is arranged at a position 30-40 mm above the sample table, the temperature of the sample table is controlled to be 5-9 ℃, the temperature of the heating wire is 230-240 ℃, and the pressure in the chemical vapor deposition chamber is 2-5 Pa.
More preferably, the vapor of t-butyl hydroperoxide and perfluorophenyl methacrylate has an inlet flow rate of 1mL/min and an inlet flow rate of 0.1 to 0.2mL/min in this order.
Further preferably, the vapor is obtained by a water bath evaporation method, wherein the tert-butyl hydroperoxide is evaporated at 25 ℃ in the water bath, and the perfluorophenyl methacrylate is evaporated at 100 ℃ in the water bath.
More preferably, the surface treatment time is 2 to 3 hours.
The composite material for treating petrochemical wastewater is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) firstly, carrying out modification treatment on magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash; then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning; then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution; finally, the fiber is placed in impregnating solution for impregnation treatment, and surface treatment is realized through surface polymerization of the perfluorophenyl methacrylate, so that the composite material is obtained. The composite material has good hydrophobicity, is suitable for petrochemical wastewater treatment, and has a good treatment effect.
(2) The main material of the invention is fiber polymerized by acrylonitrile, itaconic acid and methyl methacrylate, the macromolecular polymer itself has a certain adsorption effect, and the cyano group therein has coordination effect on heavy metals and the like and further enhances the adsorption effect. The modified magnetic fly ash is added in the polymerization process, thereby being beneficial to the cyclic utilization of industrial waste, simultaneously endowing magnetism, facilitating magnetic separation and greatly simplifying the wastewater treatment process.
(3) According to the invention, N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane, 2-pyridylaldehyde and the like are used as raw materials to prepare an impregnation liquid, fibers are placed in the impregnation liquid for impregnation treatment, so that abundant hydrophobic groups are introduced to the surfaces of the fibers, and finally surface treatment is realized through surface polymerization of perfluorophenyl methacrylate, so that the hydrophobic groups are more abundant, therefore, the obtained composite material has better hydrophobicity, and in addition, hydrogen bonds exist among introduced cyano groups, fluorine groups, amino groups and the like, so that a net structure is formed, the pores are abundant, and the adsorption effect is better.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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
A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:
(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;
(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;
(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;
(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.
The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 3kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.7kg of magnetic fly ash, heating to reflux, stirring for 2 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.
In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of the magnet is 20000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.
In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 0.8kg of itaconic acid and 10kg of methyl methacrylate into a polymerization kettle, then adding 2kg of azodiisobutyronitrile and 500kg of dimethyl sulfoxide, carrying out polymerization reaction for 6 hours at 45 ℃, then adding 10kg of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 7 hours to obtain the spinning solution.
After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment time was 30 minutes under 4 kPa.
In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.05mm to form a thin stream, and the thickness of an air layer is 25 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 6%; the coagulation bath temperature was 35 ℃.
In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3.5: 0.3: 0.8: 1.8; the mass concentration of the potassium hydroxide aqueous solution is 40%.
In the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 6 hours at 80 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 30 minutes at 50 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 70 ℃ for 22 hours.
In the step (3), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 5 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.
In the step (4), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 7kg of impregnation liquid, standing and impregnating for 3 hours, taking out and naturally airing.
In the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.
The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged 40mm above the sample table, the temperature of the sample table is controlled to be 5 ℃, the temperature of the heating wire is 240 ℃, and the pressure in the chemical vapor deposition chamber is 2 Pa.
The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.2mL/min in sequence.
The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.
The surface treatment time was 2 hours.
Example 2
A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:
(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;
(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;
(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;
(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.
The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 4kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.5kg of magnetic fly ash, heating to reflux, stirring for 3 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.
In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of magnet when initially choosing is 10000 Oe, the magnet is permanent magnet or electro-magnet.
In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 1.2kg of itaconic acid and 8kg of methyl methacrylate into a polymerization kettle, then adding 3kg of azodiisobutyronitrile and 450kg of dimethyl sulfoxide, carrying out polymerization reaction for 4 hours at 55 ℃, then adding 15kg of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 5 hours to obtain the spinning solution.
The method comprises the following steps of (1) removing monomers and removing bubbles after the polymerization reaction is finished: and treating for 20 minutes under the condition of 5 kPa.
In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.08mm to form a thin stream, and the thickness of an air layer is 22 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 8%; the coagulation bath temperature was 30 ℃.
In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3: 0.4: 0.6: 2.2; the mass concentration of the potassium hydroxide aqueous solution was 30%.
In the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 4 hours at 85 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 20 minutes at 60 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 80 ℃ for 20 hours.
In the step (3), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 7 times weight of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.
In the step (4), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 5kg of impregnation liquid, standing and impregnating for 4 hours, taking out and naturally airing.
In the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.
The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged at a position 30mm above the sample table, the temperature of the sample table is controlled to be 9 ℃, the temperature of the heating wire is 230 ℃, and the pressure in the chemical vapor deposition chamber is 5 Pa.
The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.1mL/min in sequence.
The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.
The surface treatment time was 3 hours.
Example 3
A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:
(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;
(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;
(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;
(4) and (3) finally, placing the fiber obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.
The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 3.5kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.6kg of magnetic fly ash, heating to reflux, stirring for 2.5 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.
In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of the magnet is 15000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.
In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 1kg of itaconic acid and 9kg of methyl methacrylate into a polymerization kettle, then adding 2.5kg of azobisisobutyronitrile and 480kg of dimethyl sulfoxide, carrying out polymerization reaction for 5 hours at 50 ℃, then adding 12kg of modified magnetic fly ash, and continuing to carry out polymerization reaction for 6 hours under heat preservation to obtain the spinning solution.
After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment was carried out under 4kPa for 25 minutes.
In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.06mm to form a thin stream, and the thickness of an air layer is 24 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 7%; the coagulation bath temperature was 32 ℃.
In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3.2: 0.35: 0.7: 2; the mass concentration of the potassium hydroxide aqueous solution was 35%.
In the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 5 hours at 82 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 25 minutes at 55 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 75 ℃ for 21 hours.
In the step (3), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 6 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.
In the step (4), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 6kg of impregnation liquid, standing and impregnating for 3.5 hours, taking out and naturally airing.
In the step (4), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.
The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged 35mm above the sample table, the temperature of the sample table is controlled to be 8 ℃, the temperature of the heating wire is 235 ℃, and the pressure in the chemical vapor deposition chamber is 4 Pa.
The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.15mL/min in sequence.
The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.
The surface treatment time was 2.5 hours.
Comparative example 1
A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:
(1) firstly, carrying out polymerization reaction by taking acrylonitrile, itaconic acid and methyl methacrylate as raw materials to obtain spinning solution, and spinning to obtain fibers;
(2) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;
(3) and (3) finally, placing the fiber obtained in the step (1) into the impregnation liquid obtained in the step (2) for impregnation treatment, and realizing surface treatment through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for petrochemical wastewater treatment.
In the step (1), the preparation method of the spinning solution comprises the following steps: firstly, 100kg of acrylonitrile, 0.8kg of itaconic acid and 10kg of methyl methacrylate are added into a polymerization kettle, then 2kg of azodiisobutyronitrile and 500kg of dimethyl sulfoxide are added, and polymerization reaction is carried out for 13 hours at 45 ℃ to obtain the spinning solution.
After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment time was 30 minutes under 4 kPa.
In the step (1), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.05mm to form a thin stream, and the thickness of an air layer is 25 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 6%; the coagulation bath temperature was 35 ℃.
In the step (2), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3.5: 0.3: 0.8: 1.8; the mass concentration of the potassium hydroxide aqueous solution is 40%.
In the step (2), the process conditions of the first reaction are as follows: stirring and reacting for 6 hours at 80 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 30 minutes at 50 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 70 ℃ for 22 hours.
In the step (2), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 5 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.
In the step (3), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 7kg of impregnation liquid, standing and impregnating for 3 hours, taking out and naturally airing.
In the step (3), the surface treatment method is as follows: the fiber after the dipping treatment is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.
The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged 40mm above the sample table, the temperature of the sample table is controlled to be 5 ℃, the temperature of the heating wire is 240 ℃, and the pressure in the chemical vapor deposition chamber is 2 Pa.
The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.2mL/min in sequence.
The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.
The surface treatment time was 2 hours.
Comparative example 2
A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:
(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;
(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;
(3) and (3) finally, carrying out surface treatment on the fiber obtained in the step (2) through surface polymerization of perfluorophenyl methacrylate to obtain the composite material for treating petrochemical wastewater.
The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 3kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.7kg of magnetic fly ash, heating to reflux, stirring for 2 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.
In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of the magnet is 20000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.
In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 0.8kg of itaconic acid and 10kg of methyl methacrylate into a polymerization kettle, then adding 2kg of azodiisobutyronitrile and 500kg of dimethyl sulfoxide, carrying out polymerization reaction for 6 hours at 45 ℃, then adding 10kg of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 7 hours to obtain the spinning solution.
After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment time was 30 minutes under 4 kPa.
In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.05mm to form a thin stream, and the thickness of an air layer is 25 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 6%; the coagulation bath temperature was 35 ℃.
In the step (3), the surface treatment method is as follows: the fiber is transferred into a chemical vapor deposition chamber, steam of tert-butyl hydroperoxide and perfluorophenyl methacrylate is introduced, and polymerization is carried out on the surface of the fiber to realize surface treatment.
The fiber is placed on a sample table at the bottom of a chemical vapor deposition chamber, a heating wire is arranged 40mm above the sample table, the temperature of the sample table is controlled to be 5 ℃, the temperature of the heating wire is 240 ℃, and the pressure in the chemical vapor deposition chamber is 2 Pa.
The vapor of the tert-butyl hydroperoxide and the perfluorophenyl methacrylate has inlet gas flow rates of 1mL/min and 0.2mL/min in sequence.
The steam is obtained by a water bath volatilization method, wherein tert-butyl hydroperoxide volatilizes in a water bath at 25 ℃, and perfluoro phenyl methacrylate volatilizes in a water bath at 100 ℃.
The surface treatment time was 2 hours.
Comparative example 3
A preparation method of a composite material for petrochemical wastewater treatment comprises the following specific steps:
(1) firstly, carrying out modification treatment on the magnetic fly ash by using N-phenylaminomethyl triethoxysilane to obtain modified magnetic fly ash;
(2) then, acrylonitrile, itaconic acid and methyl methacrylate are used as raw materials to carry out polymerization reaction, modified magnetic fly ash is added in the reaction process to obtain spinning solution, and fiber is obtained by spinning;
(3) then carrying out a first reaction on N-phenylaminomethyltriethoxysilane, octamethylcyclotetrasiloxane and a potassium hydroxide aqueous solution, then adding glacial acetic acid for a second reaction, then adding 2-pyridylaldehyde for a third reaction, and carrying out post-treatment to prepare an impregnation solution;
(4) and (3) finally, putting the fibers obtained in the step (2) into the impregnation liquid obtained in the step (3) for impregnation treatment to obtain the composite material for petrochemical wastewater treatment.
The specific method of the step (1) is as follows: adding 1kg of N-phenylaminomethyl triethoxysilane into 3kg of absolute ethanol, uniformly oscillating by ultrasonic waves, adding 0.7kg of magnetic fly ash, heating to reflux, stirring for 2 hours under heat preservation, and centrifuging to obtain precipitate to obtain the modified magnetic fly ash.
In the step (1), the preparation method of the magnetic fly ash comprises the following steps: firstly, grinding the steel mill fly ash into fine powder, then adopting a magnet to carry out primary selection on the fly ash, selecting magnetic particles, discarding substances with weak magnetism or no magnetism, finally cleaning the fly ash subjected to primary selection until a cleaning solution is nearly neutral so as to remove water-soluble substances, and drying the cleaned fly ash at the temperature of 60 ℃ to obtain the magnetic fly ash; the magnetic field intensity of the magnet is 20000 Oe during initial selection, and the magnet is a permanent magnet or an electromagnet.
In the step (2), the preparation method of the spinning solution comprises the following steps: adding 100kg of acrylonitrile, 0.8kg of itaconic acid and 10kg of methyl methacrylate into a polymerization kettle, then adding 2kg of azodiisobutyronitrile and 500kg of dimethyl sulfoxide, carrying out polymerization reaction for 6 hours at 45 ℃, then adding 10kg of modified magnetic fly ash, and continuing to carry out thermal polymerization reaction for 7 hours to obtain the spinning solution.
After the polymerization reaction is finished, the monomer removal and bubble removal treatment is carried out, and the specific method comprises the following steps: the treatment time was 30 minutes under 4 kPa.
In the step (2), the specific method of spinning comprises the following steps: extruding the spinning solution through a spinning nozzle to form a trickle, and allowing the trickle to enter a coagulating liquid through an air layer to perform a coagulating bath to obtain the fiber.
The spinning solution is metered by a metering pump and extruded through a spinneret with the aperture of 0.05mm to form a thin stream, and the thickness of an air layer is 25 mm.
The solidification liquid is a dimethyl sulfoxide aqueous solution with the mass concentration of 6%; the coagulation bath temperature was 35 ℃.
In the step (3), the mass ratio of N-phenylaminomethyltriethoxysilane to octamethylcyclotetrasiloxane to aqueous potassium hydroxide solution to glacial acetic acid to 2-pyridylaldehyde is 1: 3.5: 0.3: 0.8: 1.8; the mass concentration of the potassium hydroxide aqueous solution is 40%.
In the step (3), the process conditions of the first reaction are as follows: stirring and reacting for 6 hours at 80 ℃ under the protection of nitrogen; the process conditions of the second reaction are as follows: stirring and reacting for 30 minutes at 50 ℃; the process conditions of the third reaction are as follows: the reaction was stirred at 70 ℃ for 22 hours.
In the step (3), the post-treatment method comprises the following specific steps: evaporating under reduced pressure to obtain oily substance, adding the oily substance into 5 times of tetrahydrofuran, stirring to dissolve, and filtering to remove insoluble substances to obtain the immersion liquid.
In the step (4), the process conditions of the dipping treatment are as follows: adding 1kg of fiber into 7kg of impregnation liquid, standing and impregnating for 3 hours, taking out and naturally airing.
Test examples
The hydrophobic properties of the composite materials obtained in examples 1-3 and comparative examples 2 and 3 were examined, and the results are shown in Table 1.
The method for measuring the contact angle by adopting the OCA15Pro type video optical contact angle measuring instrument comprises the following steps: the injection needle model was SNS 052/026, the volume of the injection droplet (water) was 1 μ L, and the liquid profile fitting calculation used the ellipsometry. And (4) performing measurement after tabletting, selecting three different positions on the sample for measurement, and recording the intermediate value as the final experimental result.
TABLE 1 results of hydrophobic Property examination
| Contact angle (°) | |
| Example 1 | 162.3 |
| Example 2 | 163.1 |
| Example 3 | 164.5 |
| Comparative example 2 | 128.2 |
| Comparative example 3 | 134.6 |
The composite material obtained in the embodiment 1-3 or the comparative example 1-3 is used for treating petrochemical wastewater generated by a certain petrochemical enterprise, and the specific treatment method comprises the following steps: 0.1g of the composite material is added into 1L of petrochemical wastewater, the mixture is kept stand and adsorbed for 2 hours at 25 ℃, the treating agent is sucked out by an external magnet except for comparative example 1 (the comparative example 1 is filtered and taken out), and the treating agent is recycled. The wastewater treatment effect was examined and the results are shown in Table 2.
Wherein, the content of heavy metal ions is detected by a heavy metal rapid detector (FD-680 in Shanghai flight detection), COD is detected by a portable COD detector of a TE-3001 Tianer instrument, and the content of mineral oil is determined by an ultraviolet spectrophotometry.
TABLE 2 examination of COD and heavy Metal ion removal Effect
| COD removal Rate (%) | Removal rate of heavy metal ion (%) | Mineral oil removal (%) | |
| Example 1 | 99.2 | 99.1 | 99.6 |
| Example 2 | 99.5 | 99.3 | 99.7 |
| Example 3 | 99.9 | 99.6 | 99.9 |
| Comparative example 1 | 88.5 | 89.7 | 93.3 |
| Comparative example 2 | 83.7 | 84.1 | 80.1 |
| Comparative example 3 | 85.1 | 85.8 | 82.3 |
As can be seen from tables 1 and 2, the composite materials obtained in examples 1 to 3 have good hydrophobicity and good treatment effect on petrochemical wastewater.
Step (1) is omitted in comparative example 1, the impregnation treatment step of the impregnation liquid is omitted in comparative example 2, the surface polymerization of the perfluorophenyl methacrylate is omitted in comparative example 3, the treatment effect of the obtained composite material on the petrochemical wastewater is obviously deteriorated, the addition of the fly ash is helpful for improving the adsorption effect, and the hydrophobicity of the comparative examples 2 and 3 is deteriorated, so that the treatment effect on the petrochemical wastewater is influenced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
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Citations (4)
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|---|---|---|---|---|
| US4973409A (en) * | 1988-09-21 | 1990-11-27 | Ciba-Geigy Corporation | Treatment of aqueous systems |
| EP0608845A2 (en) * | 1993-01-26 | 1994-08-03 | National Starch and Chemical Investment Holding Corporation | Multifunctional maleate polymers |
| CN103693710A (en) * | 2014-01-10 | 2014-04-02 | 中国科学院新疆理化技术研究所 | Preparation and oil-water separation method of humic acid modified fly ash magnetic material |
| CN105461846A (en) * | 2014-09-05 | 2016-04-06 | 南京大学 | Magnetic acrylic-acid polyamine resin capable of removing heavy metal ions and preparation method thereof |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973409A (en) * | 1988-09-21 | 1990-11-27 | Ciba-Geigy Corporation | Treatment of aqueous systems |
| EP0608845A2 (en) * | 1993-01-26 | 1994-08-03 | National Starch and Chemical Investment Holding Corporation | Multifunctional maleate polymers |
| CN103693710A (en) * | 2014-01-10 | 2014-04-02 | 中国科学院新疆理化技术研究所 | Preparation and oil-water separation method of humic acid modified fly ash magnetic material |
| CN105461846A (en) * | 2014-09-05 | 2016-04-06 | 南京大学 | Magnetic acrylic-acid polyamine resin capable of removing heavy metal ions and preparation method thereof |
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