CN107245771B - A kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst - Google Patents

A kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst Download PDF

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CN107245771B
CN107245771B CN201710531537.4A CN201710531537A CN107245771B CN 107245771 B CN107245771 B CN 107245771B CN 201710531537 A CN201710531537 A CN 201710531537A CN 107245771 B CN107245771 B CN 107245771B
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monomer
beaker
solution
doughnut
acrylate
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CN107245771A (en
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徐乃库
张秀琴
梁炜聪
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Tianjin Polytechnic University
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    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • B01J31/063—Polymers comprising a characteristic microstructure
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
    • D06M11/485—Oxides or hydroxides of manganese; Manganates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

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  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

The invention discloses the design of complex fiber material in textile material field and manufactures, be related to a kind of preparation of hollow fiber out-phase embryonic stem-like cells catalyst, specially one kind can catalytic oxidant (such as hydrogen peroxide, ozone, persulfate) quickly, efficient oxidation decompose a variety of dyestuffs composite hollow fibre manufacturing method.The manufacturing method has mainly used a series of technologies such as basic hydrolysis, neutral potassium permanganate oxidation reduction treatment on the basis of the design of fibre-forming polymer structure, synthesis and spinning technique.Gained composite hollow fibre is compared with existing hollow fiber embryonic stem-like cells catalyst, it can repeatedly use, and with the increase of access times, composite hollow fibre catalytic activity and the decaying of dyestuff removal rate are small, time needed for reaching certain removal rate only has increased slightly, therefore, application cost is more cheap, more meets industrial applicibility requirement.

Description

A kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst
Technical field
The invention belongs to the design of complex fiber material in textile material field and manufactures, and it is different to be related to a kind of hollow fiber The preparation of phase Fenton-like catalysts, specially one kind can catalytic oxidants (such as hydrogen peroxide, ozone, persulfate) Quickly, efficient oxidation decomposes the manufacturing method of the composite hollow fibre of a variety of dyestuffs.The manufacturing method is in fibre-forming polymer structure On the basis of design, synthesis and spinning technique, a systems such as basic hydrolysis, neutral potassium permanganate oxidation reduction treatment have mainly been used Column technology.
Background technique
Water be Source of life, production want, the base of ecology, people is more, and water is few, and water resource spatial and temporal distributions unevenness is the base in China This national conditions and regimen.Currently, the situation very severe of China's Proposals of Water Resources, shortage of water resources, water pollution be serious, Ecology ring The problems such as border deteriorates becomes increasingly conspicuous, it has also become restricts the main bottleneck of Sustainable Socioeconomic Development.Water pollution control and water provide One of the strategic issue that source protection has become China at present or even the whole world is paid close attention to jointly.In recent years, with national economy Fast development, industrial wastewater pollution are on the rise, and cause water resource water quality deterioration, wherein the dyestuff that printing and dyeing industry is discharged is useless Water occupies significant proportion in industrial wastewater, these waste water from dyestuff have coloration and COD content is high, water variation greatly, alkalinity by force, The features such as complicated component and difficult for biological degradation, but also containing there are many with bio-toxicity or with carcinogenic, teratogenesis and mutagenesis Organic matter.Dyeing waste water such as cannot be handled timely and effectively, it will caused influence very serious to environment, while can also Restrict the normal development of China's economy.Therefore, dye wastewater treatment new material and new technology are developed, treatment effect is improved, is reduced Processing cost is improved the ecological environment, realize clean manufacturing have become dyestuff department, various countries and scholar research emphasis (Li Yibing, Li Jing, present Research of the Wang Lijuan .Fenton method in wastewater treatment process and progress continuing education school, Hebei University of Technology Journal, 2008,23 (3): 48-51).
Currently, the dye wastewater treatment method industrially generallyd use has: physicochemical treatment method (such as flocculent precipitation), life Object facture (such as aerobic and Anaerobic Methods in Treating).Wherein, although physicochemical treatment method has, equipment is simple, occupied area It is small, to the variation of wastewater flow rate, water temperature and concentration adapt to it is strong, can dephosphorization, denitrogenation, good decolorizing effect, management simple operation and other advantages, but Such method is generally only that the organic matters such as dyestuff are transferred to solid phase from liquid phase, for example remove pollutant suspend and dissolution and The chemical coagulation of use -- precipitating and activated carbon adsorption two-stage treatment do not completely eliminate organic pollutant from substantially saying, A large amount of solid waste and regenerative wastewater can be brought instead, and the installation cost of processing system and daily running cost are higher.Bioanalysis With processing, low energy consumption, processing cost is low, engineering is simple, can be realized sewage recycling, combines sewage treatment and utilization The advantages that, but in the presence of handling, the time is long, equipment area occupied is big, treatment effect is influenced vulnerable to natural cause and causes unstable etc. Disadvantage, and the organic pollutants such as dyestuff to biology toxic effect removal effect can be caused bad the problems such as, in anaerobic condition Under be also possible to generate carcinogenic aromatic amine compounds (Huma Hayat, Qaisar Mahmood, Arshid Pervez, Comparative decolorization of dyes in textile wastewater using biological and Chemical treatment, Separation and Purification Technology, 2015,154:149-153), Therefore, above-mentioned conventional method has been unable to satisfy the high request of environmental protection and technique at present.
Compared to the above, catalysis oxidation decomposition method is generated in high activity using chemically and physically process catalytic oxidant Mesosome (such as hydroxyl radical free radical, superoxide radical), high activity intermediate can quick oxidation dye, so that it is resolved into CO2、H2O and Other are to the mankind and environmentally friendly product, and the technology is applied widely, and the reaction time is short, and oxidability is strong, and treatment effeciency is high, Product pollution is few or pollution-free.Therefore, catalysis oxidation decomposition method has a good application prospect in water treatment field, becomes current The hot spot of water treatment field research.
Catalysis oxidation decomposition method mainly includes photocatalytic oxidation, homogeneous catalytic oxidation method and heterogeneous catalytic oxidation method etc.. Photocatalytic oxidation refers to using having photosensitive substance, under illumination condition, generates the active oxygen object with strong oxidizing property Kind, to convert small organic molecule, water and carbon dioxide etc. for the pollutant in waste water, achieve the purpose that purify sewage. Photochemical catalyst is typically all semiconductor material, for example, TiO2, it is that current use is most extensive as the photochemical catalyst of function admirable Semiconductor catalyst, but there are the following problems when photocatalysis treatment of waste water: 1. needing TiO in catalytic process2It is carried on load On body, but it is difficult to keep its high catalytic activity for a long time；②TiO2Optical response range is relatively narrow, the electron-hole pair stability of generation Difference is easy to happen the compound of phase inside and outside, influences its photocatalysis efficiency；3. the utilization rate to sunlight is not high, TiO2Forbidden band Width is only 3.2eV, can only absorb the ultraviolet portion that sunlight medium wavelength is less than 380nm, optical response range is relatively narrow, causes energy Source consumption it is big (Chen Lin, Yang Sudong, Wang Chuanyi photocatalysis material of titanium dioxide and its Research Advance in Modification Methods ion exchange with Absorption, 2013,29 (1): 86-96)；In addition, ZnO is because having and TiO2Similar forbidden bandwidth, also as a kind of common light Catalyst uses, and it is excellent to have that low in cost, preparation process is simple, non-toxic, pollution-free, low consumption, photocatalytic activity are higher etc. Point, but zinc oxide belongs to amphoteric oxide material, and dissolution reaction, zinc oxide also Yi Beiguang easily occur in highly basic and strong acid solution Corrosion, therefore, service life is limited, and (the hydrothermal synthesis method such as Han Shuai, Wang Haifang, Hou Bin, Liu Kankan prepares photochemical catalyst zinc oxide And photocatalytic degradation effect research New Chemical Materials, 2015,43 (1): 173-175).It is studied most in homogeneous catalytic oxidation method It is widely Fenton oxidation method, this method is substantially H2O2、O3Equal oxidants are in Fe2+Catalytic action under generate have height The hydroxyl radical free radical (OH) of reactivity, OH can be acted on most of organic matters makes its degradation, mild with reaction condition, Reaction time is short, Catalysis Rate is fast, reaction process is easily controllable, can a variety of dyestuffs of oxygenolysis, can voluntarily to generate flocculation etc. excellent Point, but there is also some disadvantages simultaneously for Fenton oxidation method, such as are influenced by pH, Fe2+It is easily oxidized to Fe in air3+ And inactivate, in treated water because containing Fe3+Secondary pollution etc. is caused, these disadvantages limit answering on a large scale for Fenton oxidation method With (He Xinfeng, Study on degradation of the multiphase-fenton Fenton process to methyl orange dye waste water, Shaanxi Normal University, 2011).Heterogeneous catalysis Oxidizing process is an important component in catalytic oxidation, is accelerated in liquid at normal temperatures and pressures using solid catalyst Oxidation reaction, catalyst exist in solid form, overcome the losing issue of homogeneous catalytic oxidation method catalyst, and this method is common Catalyst have Mn oxide, copper oxide and vanadium oxide etc., in these oxide catalysts, Mn oxide is as a kind of depth The catalyst of oxidation has excellent catalytic oxidation activity, in dye wastewater treatment field, MnOxWith H2O2Or peroxidation sulfuric acid Salt (PMS) reacts and generates different types of living radical, such as in MnO2/H2O2, graphene/MnO2/H2O2With carbon nanometer Pipe/γ-MnO2/H2O2OH can be generated in each system, in pyrolusite/H2O2O can be generated in system2And HO2, MnO2SO can be generated in/PMS system4, these living radicals can make dyestuff degrade (Han J, Wang M, Cao S, et al.Reactive template strategy for fabrication of MnO2/polyaniline coaxial nanocables and their catalytic application in the oxidative decolorization of Rhodamine B.Journal of Materials Chemistry A, 2013,1 (42): 13197-13202；Fathy NA, El-Shafey SE, El-Shafey OI, et al.Oxidative degradation of RB19 dye by a novel γ-MnO2/MWCNT nanocomposite catalyst with H2O2.Journal of Environmental Chemical Engineering, 2013,1 (4): 858-864；Do S H, Batchelor B, Lee HK, et Al.Hydrogen peroxide decomposition on manganese oxide (pyrolusite): kinetics, Intermediates, and mechanism.Chemosphere, 2009,75 (1): 8-12；Saputra E, Muhammad S, Sun H, et al.Different crystallographic one-dimensional MnO2nanomaterials and their superior performance in catalytic phenol degradation.Environmental Science&Technology, 2013,47 (11): 5882-5887).Manganese oxide catalyst and other above-mentioned catalysis material phases Than not only there are the advantages such as environmental protection, rich reserves, preparation process be simple and cheap, but also also have in terms of sewage treatment Whether there is or not i.e. implementable under light requirement photograph, without secondary pollution, room temperature, oxidability is strong, efficient degradation dyestuff, percent of decolourization are high, COD removal Therefore many advantages, such as rate is high has immeasurable potential value and application prospect using Mn oxide processing waste water from dyestuff. Nevertheless, Mn oxide obtained is mostly powdered or graininess at present, it is difficult to after catalysis oxidation disperse dyes direct with water Separation need to separate by means such as filtering, centrifugations, greatly improve application cost, limit its application.Therefore, research and The Mn oxide base catalysis material that developing directly to separate with water body has important practical significance.
Based on the above background, this seminar is synthesized using (methyl) acrylate substance as monomer using solution polymerization process Poly- (methyl) acrylate solution, then using the solution as spinning solution, by the filament spinning component of designed, designed, using wet process Spinning technique is prepared for poly- (methyl) the acrylate doughnut that surfaces externally and internally is rich in hydroxyl, then in water soluble alkali and It is anti-based on the redox between lye etching from outward appearance to inner essence and hydroxyl and potassium permanganate in potassium permanganate mixed solution It answers, potassium permanganate is reduced and generates Mn oxide, and hydroxyl is oxidized and generates carboxylic acid group, deposits between Mn oxide and carboxylic acid group It in strong complexing, is securely joined with the Mn oxide generated not only in fiber surfaces externally and internally, but also is carried on interior It in hole between outer surface, is made using poly- (methyl) acrylate as skeleton, Mn oxide is that the composite hollow of loaded article is fine Dimension, composite hollow fibre not only has the characteristic of catalytic oxidant oxygenolysis dyestuff, but also can directly divide with water body when application From specific surface area is also very big, therefore has many advantages, such as catalytic activity height, and processing speed is fast, dyestuff removal rate is high, with above content For inventive point, this seminar has applied for Chinese invention patent (application number: CN201610343408.8).Follow-up study discovery, on It states composite hollow fibre and there is a significant defect in application process, i.e. reusability is poor, with the increase of access times, Composite hollow fibre catalytic activity sharply declines, dyestuff removal rate sharp-decay, and the time needed for reaching certain removal rate is very big Increase, then its reusability variation reason is studied, as a result, it has been found that reason is: 1. in water soluble alkali and height In potassium manganate mixed solution, the Mn oxide of generation is birnessite type Mn oxide, and the presence of alkali metal ion causes water sodium Manganese ore type Mn oxide compared with conventional Mn oxide have weaker catalytic activity, and alkali metal ion be easy to and other from Son exchanges, and in application process, decomposes different kinds of ions with dye oxidation and generates, and then exchange with alkali metal ion, Birnessite type Mn oxide catalytic activity is caused to be poisoned；2. Inductively coupled plasma optical emission spectrometer result of study table Bright, in application process, compared with conventional Mn oxide, the manganese in birnessite type Mn oxide is easier in the form of ion It is eluted in dye solution, under comprehensive function, composite hollow fibre is caused to be difficult to reuse.Therefore, to further decrease It is imperative to improve composite hollow fibre reusability for application cost.
Summary of the invention
For the deficiency of existing 201610343408.8 technology of patent, the technical issues of present invention intends to solve, is to provide one Kind has the manufacturing method of the hollow fiber out-phase embryonic stem-like cells catalyst of fabulous reusability.The manufacturing method is first Suitable monomer first is selected on the basis of prior art invention, the polymer solution of hydroxyl is rich in using solution polymerization process preparation, Using this solution as spinning solution, doughnut is spinned using wet spinning technology, then to hollow fibre in water soluble alkali aqueous solution Dimension is hydrolyzed, after washing repeatedly through deionized water, being dry, and then among the above with neutral potassium permanganate solution processing Hollow fiber makes it that redox reaction occur with hydroxyl, and due to no longer there is water soluble alkali, potassium permanganate is reduced and generates often Advise Mn oxide, hydroxyl is oxidized and generates carboxylic acid group, between conventional Mn oxide and carboxylic acid group under strong complexing, it is obtained with Poly- (methyl) acrylate is skeleton, and conventional Mn oxide is the composite hollow fibre of loaded article.Hydrolysis under alkaline condition will A large amount of sodium carboxylate groups assign doughnut, on the one hand from outward appearance to inner essence improve the energy of the affine potassium permanganate solution of doughnut Power provides convenience for the processing of subsequent potassium permanganate solution, while can be obviously improved the ability of doughnut complexing Mn oxide, To inhibit falling off for Mn oxide to provide safeguard；On the other hand it is provided for subsequent potassium permanganate processing and final application weak Alkaline pH environment, alkalescent pH environment can significantly mitigate the oxidisability of potassium permanganate, make its redox reaction between hydroxyl It is more mild, easier to control, it is not easy to injure fibrous matrix structure, assigns the better mechanical property of finished product doughnut.It is neutral high The processing of mangaic acid aqueous solutions of potassium makes doughnut load conventional Mn oxide again.In this case, lead to patent The factor of 201610343408.8 gained composite hollow fibre reusability differences is all avoided, therefore, by of the present invention The composite hollow fibre that manufacturing method obtains has fabulous reusability, and application cost significantly reduces, and more meets industry The requirement of practicability.
The technical solution that the present invention solves the technical problem is: designing a kind of hollow fiber out-phase embryonic stem-like cells The manufacturing method of catalyst, technical process are as follows:
(1) solution polymerization process: weighing the quality monomers 1 such as two parts, places it in suitable beaker a, b, weighs respectively Monomer 2, making the ratio between gross mass of monomer 2 and two parts of monomers 1 is 0.01: 9.99~9.99: 0.01, and monomer 2 is poured into above-mentioned In beaker a, initiator is weighed, makes 0.2~2% of 2 gross mass of monomer 1 and monomer in initiator quality beaker a, and will cause Agent is added in beaker a, weighs initiator again, and current initiator quality is 0.2~2% of 1 mass of monomer in beaker b, and It is added to beaker b, opens magnetic agitation, until initiator is completely dissolved in beaker a, b, organic solvent is weighed, makes organic solvent It is 1: 5~5: 1 with the ratio between 2 gross mass of two parts of monomers 1 and monomer, and adds organic solvents into above-mentioned beaker a, opens magnetic Power stirring, keeps material mixing in beaker a uniform, then goes to solution in beaker a in polymeric kettle, is passed through nitrogen to empty polymerization Residual air in kettle opens polymeric kettle heating system, 50~100 DEG C is warming up to, at this time by the monomer 1 in beaker b containing initiator It is added drop-wise in polymeric kettle dropwise, time for adding controls within 10~60min, and after completion of dropwise addition, the reaction was continued 2~6h is obtained poly- Resulting polymers solution A is transferred in suitable beaker by polymer solution A, and sealing is spare, changes above-mentioned monomer 2 into monomer 3, Above-mentioned polymerization procedure is executed, polymer solution B is obtained, resulting polymers solution B is transferred in suitable beaker, and is sealed standby With；
The monomer 1 is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, acrylic acid hydroxypropyl One of ester；
The monomer 2 be methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid just Butyl ester, Isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, methyl Isooctyl acrylate monomer, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, methacrylic acid ten One of six esters, octadecyl methacrylate；
The monomer 3 is methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl Ester, tert-butyl acrylate, the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, n-octyl, Isooctyl acrylate monomer, propylene One of sour isodecyl ester, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate；
The initiator be benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, One of cumyl peroxide, di-t-butyl peroxide；
The organic solvent is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, toluene, dimethylbenzene, four chloroethenes One of alkene；
(2) wet spinning technology: by above-mentioned steps (1) resulting polymers solution A, B with volume ratio be 99.99: 0.01~ Mixed at 0.01: 99.99, and by mixture 0.5~3h of magnetic agitation, to be uniformly mixed, gained mixed solution is poured into In wet spinning liquid holding device, then liquid holding device is placed in vacuum drier in 25~95 DEG C and -0.07~-0.1MPa item Deaeration under part, time are 0~60min, quantify mixed solution by peristaltic pump and are transported in spinning pack, squeeze out through spinneret orifice After form hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface is contacted with the coagulator in coagulating bath, in addition, pass through peristaltic pump will Coagulator is quantitatively transported to inside hollow dynamic analysis of spinning, contacts it with hollow dynamic analysis of spinning inner surface, coagulator is by deionization The mass ratio of water and organic solvent composition, deionized water and organic solvent is 10: 0~5: 5, hollow under double diffusion effect Dynamic analysis of spinning is cured as doughnut, doughnut washed once in deionized water above, is placed in air dry oven, Dry 1~6h under the conditions of 25~50 DEG C, is made nascent doughnut；
The organic solvent is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, toluene, dimethylbenzene, four chloroethenes One of alkene；
(3) basic hydrolysis technique: weighing certain mass deionized water, place it in treatment trough, and weighing certain mass can Dissolubility alkali, making the ratio between water soluble alkali and deionized water quality is 0.1: 9.9~9.9: 0.1, adds it to above-mentioned deionized water In, stirring is completely dissolved to water soluble alkali, weighs doughnut of coming into being made from certain mass above-mentioned steps (2), is made in nascent Hollow fiber and above-mentioned water soluble alkali aqueous solution mass ratio are 1: 1~1: 1000, and nascent doughnut is placed in treatment trough, It is immersed in it in water soluble alkali aqueous solution, treatment trough temperature is increased to 20~97 DEG C, starts timing, to nascent doughnut Base extraction is carried out, the base extraction time is 30s~12h, and after treatment is washed with deionized water repeatedly until going after washing Then ionized water pH dries 3h~12h close to neutrality at room temperature, to obtain the doughnut containing sodium carboxylate groups；
The water soluble alkali is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide.
(4) neutral potassium permanganate oxidation reduction treatment technique: the potassium permanganate of certain mass is weighed, volumetric flask is placed it in In, certain volume deionized water is added, configuration concentration is the potassium permanganate solution of 0.0001~0.3mol/L, measures certain body The above-mentioned potassium permanganate solution of product, and place it in treatment trough, doughnut after hydrolysis obtained by above-mentioned steps (3) is placed in place It manages in slot, and is immersed in potassium permanganate solution, potassium permanganate solution mass ratio is 1: 1 in doughnut and treatment trough ~1: 1000, fluid temperature is 20~97 DEG C in treatment trough, and the processing time is 30s~12h, and after treatment takes out hollow fibre Dimension, is washed repeatedly with deionized water, and up to cleaning solution, there is no colors, is then placed in doughnut and is dried 1~6h at room temperature, Hollow fiber out-phase embryonic stem-like cells catalyst is made.
Compared with prior art products, the present invention is resulting using poly- (methyl) acrylate as skeleton, and Mn oxide is negative The composite hollow fibre of loading morphologically has outstanding advantage, and Mn oxide common at present is mostly powdered or graininess, After catalytic oxidant oxygenolysis dyestuff, these Mn oxides easily remain in water body, need to be by means point such as filtering, centrifugations From being also difficult to thoroughly remove from water body even with means such as filtering, centrifugations, pole for nanoscale manganese oxide catalyst Secondary pollution easily is caused to water body, and can directly be taken out from water after present invention gained composite hollow fibre use, at dry It manages or without drying process, can repeatedly utilize, significantly reduce processing cost and handle bring danger level itself, and can benefit It is processed into variform product with weaving or non-woven means, can satisfy demand of the different application field to form, Jin Erkuo Wide application field；Compared with same type wet spinning process solid fibre, present invention gained composite hollow fibre has bigger ratio Surface area can load more Mn oxides, and the efficiency of catalytic oxidant oxygenolysis dyestuff significantly improves, in addition, can be direct Carry waste water from dyestuff circulation, waste water from dyestuff inside hollow fibre flow when, can a step complete dyestuff catalysis oxidation decompose, The water body of exit outflow is water purification, and especially after pore is handled, composite hollow fibre can do filtering medium use, sieve Divide, be catalyzed the purified treatment completed under double effects to water body, degree of purification is obviously improved；With 201610343408.8 institute of patent It obtains composite hollow fibre to compare, present invention gained composite hollow fibre can repeatedly use, and with the increase of access times, multiple It closes doughnut catalytic activity and the decaying of dyestuff removal rate is small, the time needed for reaching certain removal rate only has increased slightly, because This, application cost is more cheap；Finally, in addition to this seminar research achievement, there is not yet adopting in the range of applicant's retrieval The pertinent literature report of hollow fiber out-phase embryonic stem-like cells catalyst is manufactured with technique of the present invention.
Specific embodiment
Be further discussed below the present invention below with reference to example: a kind of hollow fiber out-phase Fenton-like that the present invention designs is anti- Answer the manufacturing method (hereinafter referred to as manufacturing method) of catalyst be related to fibre-forming polymer structure design, synthesis, spinning technique and The integrated application of the series of process technologies such as basic hydrolysis, neutral potassium permanganate oxidation reduction treatment, it is intended to solve it is existing with Poly- (methyl) acrylate is skeleton, and Mn oxide is the problem of the composite hollow fibre reusability difference of loaded article, for dye Material waste water etc. water body treating containing organic matter creates new material, technical process or steps are as follows:
(1) solution polymerization process: weighing the quality monomers 1 such as two parts, places it in suitable beaker a, b, weighs respectively Monomer 2, making the ratio between gross mass of monomer 2 and two parts of monomers 1 is 0.01: 9.99~9.99: 0.01, and monomer 2 is poured into above-mentioned In beaker a, initiator is weighed, makes 0.2~2% of 2 gross mass of monomer 1 and monomer in initiator quality beaker a, and will cause Agent is added in beaker a, weighs initiator again, and current initiator quality is 0.2~2% of 1 mass of monomer in beaker b, and It is added to beaker b, opens magnetic agitation, until initiator is completely dissolved in beaker a, b, organic solvent is weighed, makes organic solvent It is 1: 5~5: 1 with the ratio between 2 gross mass of two parts of monomers 1 and monomer, and adds organic solvents into above-mentioned beaker a, opens magnetic Power stirring, keeps material mixing in beaker a uniform, then goes to solution in beaker a in polymeric kettle, is passed through nitrogen to empty polymerization Residual air in kettle opens polymeric kettle heating system, 50~100 DEG C is warming up to, at this time by the monomer 1 in beaker b containing initiator It is added drop-wise in polymeric kettle dropwise, time for adding controls within 10~60min, and after completion of dropwise addition, the reaction was continued 2~6h is obtained poly- Resulting polymers solution A is transferred in suitable beaker by polymer solution A, and sealing is spare, changes above-mentioned monomer 2 into monomer 3, Above-mentioned polymerization procedure is executed, polymer solution B is obtained, resulting polymers solution B is transferred in suitable beaker, and is sealed standby With；
(2) wet spinning technology: by above-mentioned steps (1) resulting polymers solution A, B with volume ratio be 99.99: 0.01~ Mixed at 0.01: 99.99, and by mixture 0.5~3h of magnetic agitation, to be uniformly mixed, gained mixed solution is poured into In wet spinning liquid holding device, then liquid holding device is placed in vacuum drier in 25~95 DEG C and -0.07~-0.1MPa item Deaeration under part, time are 0~60min, quantify mixed solution by peristaltic pump and are transported in spinning pack, squeeze out through spinneret orifice After form hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface is contacted with the coagulator in coagulating bath, in addition, pass through peristaltic pump will Coagulator is quantitatively transported to inside hollow dynamic analysis of spinning, contacts it with hollow dynamic analysis of spinning inner surface, coagulator is by deionization The mass ratio of water and organic solvent composition, deionized water and organic solvent is 10: 0~5: 5, hollow under double diffusion effect Dynamic analysis of spinning is cured as doughnut, doughnut washed once in deionized water above, is placed in air dry oven, Dry 1~6h under the conditions of 25~50 DEG C, is made nascent doughnut；
(3) basic hydrolysis technique: weighing certain mass deionized water, place it in treatment trough, and weighing certain mass can Dissolubility alkali, making the ratio between water soluble alkali and deionized water quality is 0.1: 9.9~9.9: 0.1, adds it to above-mentioned deionized water In, stirring is completely dissolved to water soluble alkali, weighs doughnut of coming into being made from certain mass above-mentioned steps (2), is made in nascent Hollow fiber and above-mentioned water soluble alkali aqueous solution mass ratio are 1: 1~1: 1000, and nascent doughnut is placed in treatment trough, It is immersed in it in water soluble alkali aqueous solution, treatment trough temperature is increased to 20~97 DEG C, starts timing, to nascent doughnut Base extraction is carried out, the base extraction time is 30s~12h, and after treatment is washed with deionized water repeatedly until going after washing Then ionized water pH dries 3h~12h close to neutrality at room temperature, to obtain the doughnut containing sodium carboxylate groups；
(4) neutral potassium permanganate oxidation reduction treatment technique: the potassium permanganate of certain mass is weighed, volumetric flask is placed it in In, certain volume deionized water is added, configuration concentration is the potassium permanganate solution of 0.0001~0.3mol/L, measures certain body The above-mentioned potassium permanganate solution of product, and place it in treatment trough, doughnut after hydrolysis obtained by above-mentioned steps (3) is placed in place It manages in slot, and is immersed in potassium permanganate solution, potassium permanganate solution mass ratio is 1: 1 in doughnut and treatment trough ~1: 1000, fluid temperature is 20~97 DEG C in treatment trough, and the processing time is 30s~12h, and after treatment takes out hollow fibre Dimension, is washed repeatedly with deionized water, and up to cleaning solution, there is no colors, is then placed in doughnut and is dried 1~6h at room temperature, Hollow fiber out-phase embryonic stem-like cells catalyst is made.
Monomer 1 described in manufacturing method of the present invention is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate One of propyl ester, hydroxypropyl acrylate.The effect of monomer 1 is as follows: 1. introducing hydroxyl, hydroxyl is as reducing agent, with permanganic acid Redox reaction occurs for potassium, realizes that the in-situ preparation of Mn oxide, hydroxyl are oxidized to carboxyl, carboxylic under potassium permanganate effect Base and generated in-situ Mn oxide are complexed, and realize load of the doughnut to Mn oxide；2. improving the hydrophilic of doughnut Performance, convenient for the processing of waste water from dyestuff；3. monomer conversion when polymerisation in solution is improved, the polymer molecular weight that narrows distribution, Improve the spinning spinnability of polymer.The preferred hydroxyethyl methacrylate of monomer 1 described in manufacturing method of the present invention, reason is such as Under: compared with hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate is Non-toxic Reagent is learned, harm will not be generated to human body.
Monomer 2 described in manufacturing method of the present invention is methyl methacrylate, ethyl methacrylate, methacrylic acid third Ester, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, methyl-prop Olefin(e) acid n-octyl, isooctyl methacrylate, isodecyl methacrylate, lauryl methacrylate, methacrylic acid 14 One of ester, hexadecyl metrhacrylate, octadecyl methacrylate.The effect of monomer 2 is as follows: the 1. homopolymer of monomer 2 Solution has preferable spinning spinnability, therefore the spinning spinnability of polymer solution can be improved in the introducing of monomer 2, is conducive to wet process Spinning technique；2. destroying the hydrogen bond action between monomer 1 and organic solvent, rate of polymerization is improved, inhibits the homopolymerization of monomer 1, makes to gather Zoarium system generates copolymer, in last handling process, accelerates hydrolysis of the lye to doughnut from outward appearance to inner essence, introduces more carboxylics Sour sodium group strengthens the ability of doughnut complexing Mn oxide.The preferred metering system of monomer 2 described in manufacturing method of the present invention Sour N-butyl, the reason is as follows that: 1. compared with methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl-prop Olefin(e) acid N-butyl is easier to be copolymerized with monomer 2, and smell is smaller, and reaction condition is milder, easily controllable polymerization process, no There are implode, it is highly exothermic phenomena such as；2. with Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid just oneself Ester, n octyl methacrylate, isooctyl methacrylate, isodecyl methacrylate, lauryl methacrylate, methyl-prop 14 ester of olefin(e) acid, hexadecyl metrhacrylate, octadecyl methacrylate ester are compared, and n-BMA side chain lengths are suitable Preferably, can assign polymer moderate glass transition temperature after polymerization, make it have excellent flexibility, suitable elasticity, compared with Intensity outstanding.
Monomer 3 described in manufacturing method of the present invention is methyl acrylate, ethyl acrylate, and propyl acrylate, acrylic acid are just Butyl ester, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, n-octyl, third The different monooctyl ester of olefin(e) acid, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, in octadecyl acrylate One kind.The effect of monomer 3 is as follows: 1. the homopolymer of monomer 3 has fabulous flexibility, elasticity outstanding, therefore monomer 3 draws The flexibility and elasticity for entering to substantially improve doughnut are conducive to the progress of post-processing, have final doughnut More practical mechanical property；2. destroying the hydrogen bond action between monomer 1 and organic solvent, rate of polymerization is improved, inhibits monomer 1 Homopolymerization makes polymerization system generate copolymer, in last handling process, accelerates hydrolysis of the lye to doughnut from outward appearance to inner essence, draws Enter more sodium carboxylate groups, strengthens the ability of doughnut complexing Mn oxide.Monomer 3 described in manufacturing method of the present invention is excellent N-butyl acrylate is selected, the reason is as follows that: 1. compared with methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate The polymer of generation has preferable flexibility and lower temperature resistance, and being more advantageous to improves the mechanical property of doughnut and resistance to low Warm nature energy；2. the polymer strands that n-butyl acrylate generates are best compared with isobutyl acrylate, tert-butyl acrylate, Be conducive to spinning technique；3. with the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, n-octyl, Isooctyl acrylate monomer, Isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate long alkyl chain ester phase Be short alkyl chain ester than, n-butyl acrylate, when long alkyl chain polyisocyanate polyaddition, since glass transition temperature is extremely low, generation it is poly- It is especially soft viscous to close object, the later period easily glues each other and at bulk in the reaction, or even leads to polymerization because moment, implode was agglomerating Failure, and the above problem is then not present when the polymerization of short alkyl chain ester n-butyl acrylate polymerization.
Initiator described in manufacturing method of the present invention be benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, One of tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide.1. the principle for selecting initiator includes: Half-life period initiator appropriate is selected according to polymerization temperature, keeps polymerization time moderate, selects the initiator of high activity, i.e. half-life period Shorter initiator shortens polymerization time to improve rate of polymerization, while can reduce polymerization temperature and reduce initiator amount； 2. whether pacifying it should also be taken into account that initiator has in non-toxic, use and storage process polymer quality whether there is or not influence, initiator Congruent problem, it is well known that half-life period of the di-t-butyl peroxide at 100 DEG C is 218h, and cumyl peroxide is at 115 DEG C When half-life period be 12.3h, half-life period of the tert-butyl hydroperoxide at 154.5 DEG C is 44.8h, and isopropyl benzene hydroperoxide exists Half-life period at 125 DEG C is 21h, and half-life period of the azodiisobutyronitrile at 100 DEG C is 0.1h, and benzoyl peroxide is at 125 DEG C When half-life period be 0.42h, and temperature reduce Increased Plasma Half-life, temperature increase half life.Solution polymerization process of the present invention The range of reaction temperature being related to is 50~100 DEG C, and polymerization time is within 7h, compared to other initiators, benzoyl peroxide Half-life period it is more appropriate, it is ensured that reach ideal extent of polymerization in the polymerization time being related to, and due to benzoyl peroxide first Acyl belongs to less toxic chemicals, uses and store comparatively safe, therefore the preferred benzoyl peroxide first of initiator described in manufacturing method of the present invention Acyl.
Organic solvent described in manufacturing method of the present invention is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, first One of benzene, dimethylbenzene, tetrachloro-ethylene.Compared with dimethyl acetamide, dimethyl sulfoxide, dimethylformamide dissolves this hair The ability of bright synthesized polymer is the most prominent, and when obtained polymer solution and water contacts, dimethylformamide enters water body Speed it is also relatively fast, therefore be more advantageous to dynamic analysis of spinning solidified forming；Compared with toluene, dimethylbenzene, tetrachloro-ethylene, dimethyl The toxicity of formamide is minimum, is lower toxicity product, and other organic solvents are middle high toxicity product, for these reasons, this hair The preferred dimethylformamide of organic solvent described in bright manufacturing method.
Water soluble alkali described in preparation method of the present invention is sodium hydroxide, in potassium hydroxide, lithium hydroxide, barium hydroxide It is a kind of.The preferred sodium hydroxide of water soluble alkali described in manufacturing method of the present invention, the reason is as follows that: 1. with potassium hydroxide, lithium hydroxide It compares, sodium hydroxide is cheap, is easy to get, more conducively industrial implementation；2. being post-processed compared with barium hydroxide in doughnut Cheng Zhong, though sodium hydroxide and the carbon dioxide reaction in air, product be it is water-soluble, be not easy to remain in doughnut On, doughnut can be made to be fully hydrolyzed, and the product that barium hydroxide is reacted with Carbon Dioxide in Air is not soluble in water, it is easily residual It stays on the hollow fibers, it is hydrolyzed and subsequent applications impact, be based on above-mentioned two aspects reason, manufacturing method institute of the present invention The preferred sodium hydroxide of the water soluble alkali stated.
Specific embodiment is given below, the present invention to be described in further detail, but the claim of this application protection scope is not It is limited by specific embodiment.
Comparative example
This comparative example carries out sample preparation according to technique described in patent 201610343408.8, that is, weighs two parts of 10g methyl Hydroxy-ethyl acrylate, is respectively placed in beaker a, in b, weighs 30g n-BMA, and be poured into above-mentioned beaker In a, 0.2g benzoyl peroxide is weighed, is added it in above-mentioned beaker a, is weighed 0.05g benzoyl peroxide, be added into Into above-mentioned beaker b, magnetic agitation is opened, until the benzoyl peroxide in beaker a, b is completely dissolved, hereafter, weighs 50g bis- Methylformamide is added in above-mentioned beaker a, is opened magnetic agitation, is kept the material mixing in beaker a uniform, then by beaker a Middle solution pours into polymeric kettle, is passed through nitrogen to empty remaining air in polymeric kettle, opens polymeric kettle heating system, be warming up to 85 DEG C, the hydroxyethyl methacrylate in beaker b containing initiator is added drop-wise in polymeric kettle dropwise at this time, time for adding is 0.5h, after completion of dropwise addition, the reaction was continued, and 2h moves to resulting polymers solution A in suitable beaker after reaction, sealing It is spare；Above-mentioned n-BMA is replaced with n-butyl acrylate, above-mentioned experiment is repeated and is polymerize after reaction Object solution B places it in suitable beaker, seals spare；The above-mentioned polymer solution A of 34ml, the above-mentioned polymer solution B of 6ml are taken, It is placed in suitable beaker, magnetic agitation 1h, to be uniformly mixed, uniformly mixed solution is poured into wet spinning liquid holding device In, liquid holding device is then placed in vacuum drier deaeration under the conditions of 40 DEG C and -0.1MPa, time 30min, by compacted Dynamic pump, which quantifies mixed solution, to be transported in spinning pack, and quantitative conveying speed is 0.6ml/min, is formed after spinneret orifice squeezes out Hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface are contacted with the coagulator in coagulating bath, in addition, passing through peristaltic pump for coagulator It is transported to inside hollow dynamic analysis of spinning, contacts it with hollow dynamic analysis of spinning inner surface, the speed for conveying coagulator is 0.9ml/ Min, coagulator are made of deionized water, and under double diffusion effect, hollow dynamic analysis of spinning is cured as doughnut, by doughnut It washed once above, be placed in air dry oven in deionized water, dry 1h, is made hollow fibre of coming into being under the conditions of 50 DEG C Dimension；Weigh 3.95g potassium permanganate, place it in specification be 250ml volumetric flask in, then in above-mentioned volumetric flask be added go from Sub- water, configuration concentration are the potassium permanganate solution of 0.1mol/L, measure the above-mentioned potassium permanganate solution of 9ml, place it in suitable In suitable beaker, 1g sodium hydroxide is weighed, and add it in above-mentioned beaker, opens magnetic agitation, keep sodium hydroxide completely molten Solution is made the mixed solution being made of potassium permanganate, deionized water, sodium hydroxide, places it in treatment trough, weigh 0.064g Nascent doughnut, is immersed in mixed solution, and treatment trough temperature is increased to 80 DEG C, starts timing, to nascent doughnut It is post-processed, the processing time is 30min, and after post-processing, doughnut is taken out, is washed repeatedly with deionized water, directly To there is no black particle objects to fall, then doughnut is placed in air dry oven, dry 1h, is made under the conditions of 30 DEG C Hollow fiber embryonic stem-like cells catalyst.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% after 90min；Containing 10ml concentration in the wide-mouth bottle marked as a, b, c respectively is 20mg/ The above-mentioned hollow fiber embryonic stem-like cells catalyst of 0.024g is first placed in wide-mouth bottle a, adds by the cationic blue aqueous solution of L Enter 500ul hydrogen peroxide, under the conditions of magnetic agitation, when cationic blue removal rate is up to 90% the time required to be 40min, continue magnetic force Stirring, cationic blue removal rate is up to 94.48% when 90min, then by hollow fiber embryonic stem-like cells catalyst from wide It takes out in mouth bottle a, after drying at room temperature 2h, is put into the wide-mouth bottle b for filling cationic blue aqueous solution, 500ul hydrogen peroxide is added, Under the conditions of magnetic agitation, the removal rate of cationic blue is up to 79.30% when 90min, according to above-mentioned repeated using method, to wide-mouth Cationic blue aqueous solution in bottle c is handled, and the removal rate of cationic blue is up to 57.23% when 90min.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 500ul hydrogen peroxide is added, lmin ozone is passed through, in magnetic Under power stirring condition, the removal rate of methylene blue dye is 0.12% when 90min；By the above-mentioned hollow fiber Fenton-like of 0.1g Catalysts are placed in the aqueous solution of methylene blue that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide is added, it is smelly to be passed through 1min Oxygen, under the conditions of magnetic agitation, the removal rate of methylene blue is up to 83.29% when 90min.
The gorgeous blue aqueous solution of weak acid that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, 1min ozone is passed through, in magnetic Under power stirring condition, the removal rate of the gorgeous blue dyestuff of weak acid is 20.89% when 90min；By the above-mentioned hollow fiber class of 0.1g Fenton catalysts are placed in the gorgeous blue aqueous solution of weak acid that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide is added, is passed through 1min ozone, under the conditions of magnetic agitation, the removal rate of the gorgeous orchid of weak acid is up to 46.89% when 90min.
Embodiment 1
Embodiment 1 is the embodiment obtained after optimization preparation process in embodiment 2 to 13 Research foundation of embodiment, and It is compared with comparative example using result, with the advantage of prominent present invention gained technical products.
Two parts of 10g hydroxyethyl methacrylates are weighed, are respectively placed in beaker a, in b, are weighing 30g methacrylic acid just Butyl ester, and be poured into above-mentioned beaker a, 0.2g benzoyl peroxide is weighed, and add it in above-mentioned beaker a, weighed 0.05g benzoyl peroxide adds it in above-mentioned beaker b, opens magnetic agitation, until the benzoyl peroxide in beaker a, b Formyl is completely dissolved, and hereafter, weighs 50g dimethylformamide, is added in above-mentioned beaker a, is opened magnetic agitation, is made beaker a In material mixing it is uniform, then solution in beaker a is poured into polymeric kettle, is passed through nitrogen to empty remaining sky in polymeric kettle Gas opens polymeric kettle heating system, is warming up to 85 DEG C, dropwise by the hydroxyethyl methacrylate in beaker b containing initiator at this time It is added drop-wise in polymeric kettle, time for adding 0.5h, after completion of dropwise addition, the reaction was continued 2h is after reaction, molten by resulting polymers Liquid A is moved in suitable beaker, is sealed spare；Above-mentioned n-BMA is replaced with n-butyl acrylate, is repeated above-mentioned Experiment, after reaction, obtains polymer solution B, places it in suitable beaker, seals spare；Take the above-mentioned polymer of 34ml Solution A, the above-mentioned polymer solution B of 6ml, is placed in suitable beaker, magnetic agitation 1h, to be uniformly mixed, will be uniformly mixed Solution pour into wet spinning liquid holding device, then liquid holding device is placed in vacuum drier in 40 DEG C and -0.1MPa item Deaeration under part, time 30min, mixed solution is quantified be transported to by peristaltic pump in spinning pack, and quantitative conveying speed is 0.6ml/min forms hollow dynamic analysis of spinning, the coagulator in hollow dynamic analysis of spinning outer surface and coagulating bath after spinneret orifice squeezes out Contact, in addition, coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump, connects it with hollow dynamic analysis of spinning inner surface Touching, the speed for conveying coagulator is 0.9ml/min, and coagulator is made of deionized water, and under double diffusion effect, hollow spinning is thin Stream is cured as doughnut, doughnut washed once in deionized water above, is placed in air dry oven, at 50 DEG C Under the conditions of dry 1h, nascent doughnut is made；7ml deionized water is measured with graduated cylinder, places it in suitable beaker, weighs 3g sodium hydroxide adds it in above-mentioned deionized water, and stirring is completely dissolved to sodium hydroxide, places it in treatment trough, 0.064g as-spun fibre is weighed, is immersed in it in sodium hydroxide solution, treatment trough temperature is increased to 80 DEG C, starts timing, Nascent doughnut is hydrolyzed, the processing time is 6h, and after treatment is washed with deionized water repeatedly until washing Deionized water pH is close neutral afterwards, then drying at room temperature 3h；3.95g potassium permanganate is weighed, placing it in specification is 250ml capacity In bottle, then to deionized water is added in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1mol/L, is measured The above-mentioned potassium permanganate solution of 10ml, and it is molten that fiber of the above-mentioned sodium hydroxide solution processing after dry be immersed in this potassium permanganate It in liquid, places it in treatment trough, treatment trough temperature is increased to 80 DEG C, starts timing, to the doughnut after base extraction It is post-processed, after post-processing, doughnut is taken out by finishing time 5.5h, is washed repeatedly with deionized water, directly To there is no black particle objects to fall, doughnut is then dried at room temperature for 2h, hollow fiber out-phase class is made Fenton catalysts.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, The removal rate of cationic blue is 16.24% when 90min；10ml is contained in the wide-mouth bottle marked as 1#, 2#, 3#, 4#, 5# respectively Concentration is the cationic blue aqueous solution of 20mg/L, and the above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is first set In wide-mouth bottle 1#, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, when cationic blue removal rate is up to 90% the time required to For 7min, continue magnetic agitation, cationic blue removal rate is up to 97.48% when 90min, then by hollow fiber out-phase class Fenton catalysts take out from wide-mouth bottle 1#, after drying at room temperature 2h, are put into the wide-mouth bottle for filling cationic blue aqueous solution In 2#, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, when cationic blue removal rate is up to 90% the time required to be 28min, Continue magnetic agitation, cationic blue removal rate is up to 98.20% when 90min, according to above-mentioned repeated using method, successively to wide-mouth Cationic blue aqueous solution is handled in bottle 3#, 4#, 5#, when 90min the removal rate of cationic blue water respectively up to 58.75%, 37.08%, 24.16%.Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, 50ul hydrogen peroxide is added, in magnetic agitation Under the conditions of, cationic blue removal rate is 6.66% when 90min；It is contained in the wide-mouth bottle marked as 1#, 2#, 3#, 4#, 5# respectively 10ml concentration is the cationic blue aqueous solution of 20mg/L, by the above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g It is first placed in wide-mouth bottle 1#, 50ul hydrogen peroxide is added, under the conditions of magnetic agitation, taken when cationic blue removal rate is up to 90% Between be 4min, continue magnetic agitation, cationic blue removal rate is up to 97.20% when 90min, then by hollow fiber out-phase class Fenton catalysts take out from wide-mouth bottle 1#, after drying at room temperature 2h, are put into the wide-mouth bottle for filling cationic blue aqueous solution In 2#, 50ul hydrogen peroxide is added, under the conditions of magnetic agitation, required time is 12min when cationic blue removal rate reaches 90%, Continue magnetic agitation, cationic blue removal rate is up to 96.71% when 90min, according to above-mentioned repeated using method, successively to wide-mouth Cationic blue aqueous solution is handled in bottle 3#, 4#, 5#, when 90min cationic blue removal rate respectively up to 96.94%, 93.71%, 65.40%.The sun that 10ml concentration is 20mg/L is contained in the wide-mouth bottle marked as 1#, 2#, 3#, 4#, 5# respectively The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is first placed in wide-mouth bottle 1# by ion indigo plant aqueous solution, Under the conditions of magnetic agitation, when cationic blue removal rate reaches 90% the time required to be 18min, continue magnetic agitation, sun when 90min Then ion indigo plant removal rate takes hollow fiber out-phase embryonic stem-like cells catalyst up to 95.73% from wide-mouth bottle 1# Out, it after drying at room temperature 2h, is put into the wide-mouth bottle 2# for filling cationic blue aqueous solution, under the conditions of magnetic agitation, cationic blue It is 20min the time required to when removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 96.49%, according to above-mentioned repeated using method, successively cationic blue aqueous solution in wide-mouth bottle 3#, 4#, 5# is handled, sun It is respectively 17min, 21min, 25min the time required to when ion indigo plant removal rate reaches 90%, continues magnetic agitation, sun when 90min Ion indigo plant removal rate is respectively up to 97.72%, 98.02%, 97.80%.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, The removal rate of methylene blue is 4.82% when 90min；By the above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g It is placed in the aqueous solution of methylene blue that 10ml concentration is 20mg/L, 500ul hydrogen peroxide, under the conditions of magnetic agitation, methylene is added It is 30min the time required to when base indigo plant removal rate is up to 90%, continues magnetic agitation, methylene blue removal rate is reachable when 90min 96.65%.
The gorgeous blue aqueous solution of weak acid that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, The removal rate of the gorgeous orchid of weak acid is 21.03% when 90min；By the above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g It is placed in the gorgeous blue aqueous solution of weak acid that 10ml concentration is 20mg/L, 500ul hydrogen peroxide, under the conditions of magnetic agitation, weak acid is added It is 8min the time required to when gorgeous orchid removal rate reaches 90%, continues magnetic agitation, the gorgeous blue removal rate of weak acid is reachable when 90min 96.39%.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 50ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 6.66% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.012g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 50ul hydrogen peroxide, under the conditions of magnetic agitation, cationic blue is added It is 9min the time required to when removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is up to 96.02% when 90min； The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.036g is placed in the cationic blue water that 10ml concentration is 20mg/L In solution, 50ul hydrogen peroxide is added, under the conditions of magnetic agitation, required time is when cationic blue removal rate reaches 90% 4min continues magnetic agitation, and cationic blue removal rate is up to 97.20% when 90min；By the above-mentioned hollow fiber out-phase of 0.048g Embryonic stem-like cells catalyst is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, 50ul hydrogen peroxide is added, in magnetic Under power stirring condition, when cationic blue removal rate reaches 90% the time required to be 3min, continue magnetic agitation, when 90min sun from Sub- indigo plant removal rate is up to 96.34%.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；It is contained in the wide-mouth bottle marked as 1,2,3,4,5,6,7,8,9,10 respectively 10ml concentration is the cationic blue aqueous solution of 20mg/L, by the above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g It is first placed in wide-mouth bottle 1,500ul hydrogen peroxide is added, under the conditions of magnetic agitation, taken when cationic blue removal rate is up to 90% Between only 12min, then hollow fiber out-phase embryonic stem-like cells catalyst is taken out from wide-mouth bottle 1, and is immediately placed in wide In mouthful bottle 2,500ul hydrogen peroxide is added, under the conditions of magnetic agitation, when cationic blue removal rate is up to 90% the time required to only 18min, according to above-mentioned repeated using method, successively to cationic blue aqueous solution in wide-mouth bottle 3,4,5,6,7,8,9,10 at Reason, when cationic blue removal rate is up to 90% the time required to be followed successively by 29,61,77,84,107,172,219,279min.Take 10ml Concentration is the cationic blue aqueous solution of 20mg/L, and 50ul hydrogen peroxide is added, under the conditions of magnetic agitation, cationic blue when 90min Removal rate is 6.66%；Containing 10ml concentration in the wide-mouth bottle marked as 1,2,3,4,5,6,7,8,9,10 respectively is 20mg/L Cationic blue aqueous solution, the above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is first placed in wide-mouth bottle 1, 50ul hydrogen peroxide is added, under the conditions of magnetic agitation, when cationic blue removal rate is up to 90% the time required to only 6.5min, then will Hollow fiber out-phase embryonic stem-like cells catalyst takes out from wide-mouth bottle 1, and is immediately placed in wide-mouth bottle 2, and 50ul is added Hydrogen peroxide, under the conditions of magnetic agitation, when cationic blue removal rate is up to 90% the time required to only 10min, make according to above-mentioned repetition With method, successively cationic blue aqueous solution in wide-mouth bottle 3,4,5,6,7,8,9,10 is handled, cationic blue removal rate reaches 18,35.5,36.5,42,56,82.5,92.5,140min are followed successively by the time required to when 90%.Respectively marked as 1,2,3,4, 5, the cationic blue aqueous solution that 10ml concentration is 20mg/L is contained in 6,7,8,9,10 wide-mouth bottle, by the above-mentioned hollow fibre of 0.048g Dimension shape out-phase embryonic stem-like cells catalyst is first placed in wide-mouth bottle 1, and 50ul hydrogen peroxide is added, under the conditions of magnetic agitation, sun Only 3min the time required to when ion indigo plant removal rate is up to 90%, then by hollow fiber out-phase embryonic stem-like cells catalyst from wide It takes out, and is immediately placed in wide-mouth bottle 2 in mouth bottle 1,50ul hydrogen peroxide is added, under the conditions of magnetic agitation, cationic blue removal Only 4.5min the time required to when rate is up to 90%, according to above-mentioned repeated using method, successively to wide-mouth bottle 3,4,5,6,7,8,9,10 Middle cationic blue aqueous solution is handled, when cationic blue removal rate is up to 90% the time required to be followed successively by 4.5,5.5,6,6.5,7, 7.5,7.5,8min.Containing 10ml concentration in the wide-mouth bottle marked as 1,2,3,4,5,6,7,8,9,10 respectively is 20mg/L's The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.072g is first placed in wide-mouth bottle 1, adds by cationic blue aqueous solution Enter 50ul hydrogen peroxide, under the conditions of magnetic agitation, when cationic blue removal rate is up to 90% the time required to only 3min, then will be hollow Fibrous out-phase embryonic stem-like cells catalyst takes out from wide-mouth bottle 1, and is immediately placed in wide-mouth bottle 2, and 50ul dioxygen is added Water, under the conditions of magnetic agitation, when cationic blue removal rate is up to 90% the time required to only 3.5min, according to above-mentioned reuse side Method is successively handled cationic blue aqueous solution in wide-mouth bottle 3,4,5,6,7,8,9,10, and cationic blue removal rate is up to 90% When the time required to be followed successively by 4.5,4.5,4.5,5,5,5.5,6,6min.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；It is contained in the wide-mouth bottle marked as 1,2,3,4,5,6,7,8,9,10 respectively 10ml concentration is the cationic blue aqueous solution of 20mg/L, by the above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g It is first placed in wide-mouth bottle 1,500ul hydrogen peroxide, magnetic agitation 10min is added, cationic blue removal rate then will up to 91.34% Hollow fiber out-phase embryonic stem-like cells catalyst takes out from wide-mouth bottle 1, and is immediately placed in wide-mouth bottle 2, and 500ul is added Hydrogen peroxide, magnetic agitation 10min, cationic blue removal rate is up to 70.40%, according to above-mentioned repeated using method, successively to wide-mouth Cationic blue aqueous solution is handled in bottle 3,4,5,6,7,8,9,10, equal magnetic agitation 10min, cationic blue removal rate difference Up to 57.96%, 42.83%, 37.32%, 35.34%, 34.45%, 31.25%, 30.44%, 30.03%.Take 10ml concentration For the cationic blue aqueous solution of 20mg/L, 50ul hydrogen peroxide is added, under the conditions of magnetic agitation, cationic blue removes when 90min Rate is 6.66%；The sun that 10ml concentration is 20mg/L is contained in the wide-mouth bottle marked as 1,2,3,4,5,6,7,8,9,10 respectively The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is first placed in wide-mouth bottle 1 by ion indigo plant aqueous solution, is added 50ul hydrogen peroxide, magnetic agitation 10min, cationic blue removal rate is up to 94.64%, then by hollow fiber out-phase Fenton-like Catalysts take out from wide-mouth bottle 1, and are immediately placed in wide-mouth bottle 2, and 50ul hydrogen peroxide, magnetic agitation 10min, sun is added Ion indigo plant removal rate is up to 91.44%, according to above-mentioned repeated using method, successively to 3,4,5,6,7,8,9,10 middle-jiao yang, function of the spleen and stomach of wide-mouth bottle from Sub- indigo plant aqueous solution is handled, magnetic agitation 10min, cationic blue removal rate respectively up to 86.74%, 79.64%, 71.09%, 61.96%, 60.98%, 55.65%, 56.49%, 46.93%.Respectively wide marked as 1,2,3,4,5,6,7,8,9,10 The cationic blue aqueous solution that 10ml concentration is 20mg/L is contained in mouth bottle, by the above-mentioned hollow fiber out-phase Fenton-like of 0.048g Catalysts are first placed in wide-mouth bottle 1, and 50ul hydrogen peroxide, magnetic agitation 10min is added, and cationic blue removal rate reaches 97.83%, then hollow fiber out-phase embryonic stem-like cells catalyst is taken out from wide-mouth bottle 1, and be immediately placed in wide-mouth In bottle 2,50ul hydrogen peroxide is added, magnetic agitation 10min, cationic blue removal rate is up to 93.40%, according to above-mentioned reuse side Method is successively handled cationic blue aqueous solution in wide-mouth bottle 3,4,5,6,7,8,9,10, magnetic agitation 10min, cation Blue removal rate respectively up to 93.26%, 94.35%, 93.10%, 94.20%, 92.26%, 90.20%, 87.88%, 82.12%.Respectively in the wide-mouth bottle marked as 1,2,3,4,5,6,7,8,9,10 contain 10ml concentration be 20mg/L sun from Sub- indigo plant aqueous solution, the above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.072g is first placed in wide-mouth bottle 1, is added 50ul hydrogen peroxide, magnetic agitation 10min, cationic blue removal rate is up to 95.66%, then by hollow fiber out-phase Fenton-like Catalysts take out from wide-mouth bottle 1, and are immediately placed in wide-mouth bottle 2, and 50ul hydrogen peroxide, magnetic agitation 10min, sun is added Ion indigo plant removal rate is up to 96.16%, according to above-mentioned repeated using method, successively to 3,4,5,6,7,8,9,10 middle-jiao yang, function of the spleen and stomach of wide-mouth bottle from Sub- indigo plant aqueous solution is handled, magnetic agitation 10min, cationic blue removal rate respectively up to 95.92%, 96.14%, 97.44%, 97.44%, 97.42%, 97.63%, 96.71%, 97.04%.
Embodiment 2
The present embodiment technical process and parameter are same as Example 1, only change deionized water by the 7ml in embodiment 1 For 9ml, and sodium hydroxide quality changes into 1g by the 3g in embodiment 1.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；Containing 10ml concentration in the wide-mouth bottle marked as A, B, C respectively is 20mg/ The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is first placed in wide-mouth bottle A by the cationic blue aqueous solution of L In, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, required time is 12min when cationic blue removal rate reaches 90%, Continue magnetic agitation, cationic blue removal rate is then anti-by hollow fiber out-phase Fenton-like up to 96.74% when 90min It answers catalyst to take out from wide-mouth bottle A, after drying at room temperature 2h, is put into the wide-mouth bottle B for filling cationic blue aqueous solution, be added 500ul hydrogen peroxide, under the conditions of magnetic agitation, required time is 50min when cationic blue removal rate reaches 90%, continues magnetic force Stirring, cationic blue removal rate is up to 96.13% when 90min, according to above-mentioned repeated using method, to cationic in wide-mouth bottle C Blue aqueous solution is handled, and cationic blue removal rate is up to 87.42% when 90min.
Embodiment 3
The present embodiment technical process and parameter are same as Example 1, only change deionized water by the 7ml in embodiment 1 For 8ml, and sodium hydroxide quality changes into 2g by the 3g in embodiment 1.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 11min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 96.56%.
Embodiment 4
The present embodiment technical process and parameter are same as Example 1, only change deionized water by the 7ml in embodiment 1 For 6ml, and sodium hydroxide quality changes into 4g by the 3g in embodiment 1.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 22min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 95.26%.
Embodiment 5
The present embodiment technical process and parameter are same as Example 1, are only adjusted to hydrolysis time by the 6h in embodiment 1 3h。
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 40min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 92.72%.
Embodiment 6
The present embodiment technical process and parameter are same as Example 1, are only adjusted to hydrolysis time by the 6h in embodiment 1 9h。
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 7min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 98.65%.
Embodiment 7
The present embodiment technical process and parameter are same as Example 1, are only adjusted to hydrolysis time by the 6h in embodiment 1 12h。
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 8min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 96.75%.
Embodiment 8
The present embodiment technical process and parameter are same as Example 1, only by liquor potassic permanganate concentration by embodiment 1 0.1mol/L changes into 0.01mol/L.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 22min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 96.75%.
Embodiment 9
The present embodiment technical process and parameter are same as Example 1, only by liquor potassic permanganate concentration by embodiment 1 0.1mol/L changes into 0.05mol/L.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 10min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 97.90%.
Embodiment 10
The present embodiment technical process and parameter are same as Example 1, only by liquor potassic permanganate concentration by embodiment 1 0.1mol/L changes into 0.2mol/L.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 18min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 90.51%.
Embodiment 11
The present embodiment technical process and parameter are same as Example 1, only by the potassium permanganate processing time by embodiment 1 5.5h changes into 30min.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 13min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 98.64%.
Embodiment 12
The present embodiment technical process and parameter are same as Example 1, only by the potassium permanganate processing time by embodiment 1 5.5h changes into 3h.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 11min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 97.28%.
Embodiment 13
The present embodiment technical process and parameter are same as Example 1, only by the potassium permanganate processing time by embodiment 1 5.5h changes into 8h.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, Cationic blue removal rate is 16.24% when 90min；The above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst of 0.024g is set In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cation It is 11min the time required to when blue removal rate reaches 90%, continues magnetic agitation, cationic blue removal rate is reachable when 90min 96.07%.

Claims (4)

1. a kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst, it is characterised in that technical process is as follows:
(1) solution polymerization process: weighing the quality monomers 1 such as two parts, is placed it in suitable beaker a, b respectively, weighs monomer 2, making the ratio between gross mass of monomer 2 and two parts of monomers 1 is 0.01: 9.99~9.99: 0.01, and monomer 2 is poured into above-mentioned beaker a In, initiator is weighed, makes 0.2~2% of 2 gross mass of monomer 1 and monomer in initiator quality beaker a, and initiator is added Enter into beaker a, weighs initiator again, current initiator quality is 0.2~2% of 1 mass of monomer in beaker b, and is added To beaker b, magnetic agitation is opened, until initiator is completely dissolved in beaker a, b, organic solvent is weighed, makes organic solvent and two Part the ratio between monomer 1 and 2 gross mass of monomer are 1: 5~5: 1, and are added organic solvents into above-mentioned beaker a, open magnetic force and stir It mixes, keeps material mixing in beaker a uniform, then go to solution in beaker a in polymeric kettle, be passed through nitrogen to empty in polymeric kettle Residual air opens polymeric kettle heating system, is warming up to 50~100 DEG C, dropwise by the monomer 1 in beaker b containing initiator at this time It is added drop-wise in polymeric kettle, time for adding controls within 10~60min, and after completion of dropwise addition, the reaction was continued 2~6h obtains polymer Resulting polymers solution A is transferred in suitable beaker by solution A, and sealing is spare, changes above-mentioned monomer 2 into monomer 3, is executed Above-mentioned polymerization procedure obtains polymer solution B, resulting polymers solution B is transferred in suitable beaker, and seals spare；Institute The monomer 1 stated is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, one in hydroxypropyl acrylate Kind；The monomer 2 is methyl methacrylate, ethyl methacrylate, propyl methacrylate, the positive fourth of methacrylic acid Ester, Isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, methyl-prop The different monooctyl ester of olefin(e) acid, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, methacrylic acid 16 One of ester, octadecyl methacrylate；The monomer 3 is methyl acrylate, ethyl acrylate, propyl acrylate, third Olefin(e) acid N-butyl, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, acrylic acid are just Monooctyl ester, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, acrylic acid One of octadecyl ester；The organic solvent is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, toluene, diformazan One of benzene, tetrachloro-ethylene；
(2) wet spinning technology: by above-mentioned steps (1) resulting polymers solution A, B with volume ratio for 99.99: 0.01~0.01: 99.99 are mixed, and by mixture 0.5~3h of magnetic agitation, and to be uniformly mixed, gained mixed solution is poured into Wet-spinning In silk liquid holding device, then liquid holding device is placed in vacuum drier and is taken off under the conditions of 25~95 DEG C and -0.07~-0.1MPa Bubble, time are 0~60min, quantify mixed solution by peristaltic pump and are transported in spinning pack, are formed after spinneret orifice squeezes out Hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface are contacted with the coagulator in coagulating bath, in addition, passing through peristaltic pump for coagulator It is quantitatively transported to inside hollow dynamic analysis of spinning, contacts it with hollow dynamic analysis of spinning inner surface, coagulator is by deionized water and has The mass ratio of solvent composition, deionized water and organic solvent is 10: 0~5: 5, and under double diffusion effect, hollow spinning is thin Stream is cured as doughnut, doughnut washed once in deionized water above, is placed in air dry oven, 25~ Dry 1~6h under the conditions of 50 DEG C, is made nascent doughnut；
(3) basic hydrolysis technique: weighing certain mass deionized water, place it in treatment trough, weighs certain mass solubility Alkali, making the ratio between water soluble alkali and deionized water quality is 0.1: 9.9~9.9: 0.1, adds it in above-mentioned deionized water, stirs It mixes to water soluble alkali and is completely dissolved, weigh doughnut of coming into being made from certain mass above-mentioned steps (2), make nascent doughnut It is 1: 1~1: 1000 with above-mentioned water soluble alkali aqueous solution mass ratio, and nascent doughnut is placed in treatment trough, makes its leaching Not in water soluble alkali aqueous solution, treatment trough temperature is increased to 20~97 DEG C, starts timing, alkali is carried out to nascent doughnut Liquid processing, base extraction time are 30s~12h, and after treatment washs the deionized water after washing with deionized water repeatedly Then pH dries 3h~12h close to neutrality at room temperature, to obtain the doughnut containing sodium carboxylate groups；
(4) neutral potassium permanganate oxidation reduction treatment technique: weighing the potassium permanganate of certain mass, place it in volumetric flask, Certain volume deionized water is added, configuration concentration is the potassium permanganate solution of 0.0001~0.3mol/L, measures certain volume Above-mentioned potassium permanganate solution, and place it in treatment trough, doughnut after hydrolysis obtained by above-mentioned steps (3) is placed in processing In slot, and be immersed in potassium permanganate solution, in doughnut and treatment trough potassium permanganate solution mass ratio be 1: 1~ 1: 1000, fluid temperature is 20~97 DEG C in treatment trough, and the processing time is 30s~12h, after treatment, taking-up doughnut, It is washed repeatedly with deionized water, up to cleaning solution, there is no colors, and then doughnut is placed in and dries 1~6h at room temperature, system Obtain hollow fiber out-phase embryonic stem-like cells catalyst.
2. a kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, special Sign be the initiator be benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, One of cumyl peroxide, di-t-butyl peroxide.
3. a kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, special Sign is that the water soluble alkali is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide.
4. a kind of system of hollow fiber out-phase embryonic stem-like cells catalyst described in any one of claim 1 to 3 Make method, it is characterised in that the monomer 1 is hydroxyethyl methacrylate, and the monomer 2 is n-BMA, The monomer 3 is n-butyl acrylate, and the initiator is benzoyl peroxide, and the organic solvent is dimethyl methyl Amide, the water soluble alkali are sodium hydroxide.
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