CN107308988B - 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 PDFInfo
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- CN107308988B CN107308988B CN201710531539.3A CN201710531539A CN107308988B CN 107308988 B CN107308988 B CN 107308988B CN 201710531539 A CN201710531539 A CN 201710531539A CN 107308988 B CN107308988 B CN 107308988B
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- 238000011010 flushing procedure Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
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 acidic 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
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 acidic hydrolysis, neutral potassium permanganate oxidation reduction treatment have mainly been used
Column technology.
Background technique
China is manufacturing industry base important in the world, but production method is based on extensive style at present, and environment situation is very
It is severe, wherein strong industry of the textile industry as China occupies very important ground in national economy and international trade
Position.According to statistics, it is about 1,600,000,000 tons that China generates dyeing waste water every year, discharged volume of industrial waste water the 6th is occupied, with processing technology
Development and new dye, auxiliary agent continually develop application, the processing difficulty of dyeing waste water also increasing.Dyeing waste water has water
The features such as amount is big, organic pollutant content is high, coloration is deep, alkalinity is big, change of water quality is big, belongs to intractable industrial wastewater (Yang
Q, Wang J, Wang H, et al, Evolution of the microbial community in a full-scale
Printing and dyeing wastewater treatment system, Bioresource Technology, 2012,
117 (4): 155-163；Lu Hongyu, Marvin's is at, beam etc., catalytic ozonation technique advanced treatment of dyeing wastewater, environmental project
Journal, 2013,7 (8): 2873-2876).In these dyeing waste waters, dye component is complicated, and concentration and coloration are higher, Er Qie great
Most difficult for biological degradation, also containing there are many with bio-toxicity or with carcinogenic, teratogenesis and mutagenic organic matter, therefore,
Treatment of dyeing wastewater causes global highest attention.
In general, the method for being commercially used for processing dyeing waste water has: physical chemistry (such as adsorb, flocculate) and biology side
Method, wherein physico-chemical process has many advantages, such as that equipment is simple, easy to operate, but such method is usually that dyestuff etc. is organic
Object is transferred to solid phase (such as active carbon adsorption) from liquid phase, does not completely eliminate organic pollutant, and can bring a large amount of solid
Body waste and regenerative wastewater, therefore, removal effect and in terms of have the defects that it is certain.Biochemical method
Equipment is simple and convenient to operate, operating cost is low, but long processing period, equipment area occupied are big, can be because of organic contaminations such as dyestuffs
Object cannot effectively remove biological toxic effect, be also possible to generate carcinogenic aromatic amine chemical combination under conditions of anaerobism
Object.It is compared to the above, high-level oxidation technology by generation strong oxidizing property living radical (such as hydroxyl radical free radical, super oxygen
Free radical etc.) by various dye oxidations, and then resolve into dye molecule to the mankind and environmentally friendly small-molecule substance (such as water
With carbon dioxide etc.), and have many advantages, such as that the reaction time is short, treatment effeciency is high, product not will cause secondary pollution, it is therefore, high
Grade oxidation technology increasingly causes the concern of people.
High-level oxidation technology usually has: Ozonation, Fenton reagent oxidizing process, photochemical oxidation method, photochemical catalytic oxidation
Method etc..
Ozonation is can instantaneously to complete the oxygen to organic pollutants such as dyestuffs at low concentrations using ozone as oxidant
Change degradation, it is without secondary pollution, but that there are ozone generating apparatus is expensive, cost for wastewater treatment is high, is not suitable for big flow waste water
The disadvantages of processing.Fenton reagent oxidizing process uses Fe2+(Fe3+)/H2O2As catalytic oxidation system, oxidation mechanism is H2O2With
Fe2+(Fe3+) reaction generation strong oxidizing property hydroxyl radical free radical (its oxidation-reduction potential is up to+2.8V), oxidation-degradable dyestuff etc.
Organic pollutant, but due to containing Fe in Fenton reagent2+(Fe3+), if solution system pH > 3.5, Fe2+(Fe3+) Fe can be generated
(OH)2Or Fe (OH)3Precipitating, causes reaction efficiency to reduce, and contains relatively large Fe in water2+(Fe3+), it will lead to secondary dirt
Dye.Photochemical oxidation method frequently with oxidation system be H2O2/UV、O3/UV、H2O2/O3/ UV etc. is a kind of light of no catalyst
Chemical reaction, the technology have the advantages that it is easy to operate, without secondary pollution, can the protrusion such as permineralization organic matter, but there is also anti-
The disadvantages of long, costly between seasonable.Photocatalytic oxidation inherits the advantages of photochemical oxidation method, while introducing catalyst again,
Reaction efficiency is greatly accelerated, especially with TiO2Research as photochemical catalyst is by (Asahi, the R. of attracting attention extensively；
Morikawa, T.；Ohwaki.T.Visible-light photocatalysis in nitrogen doped titanium
Oxides.Science, 200l, 193,269-271；Zhao, W.；Ma, W.H.；Chen, C.C.；Zhao, J.C.；Shuai,
Z.G.Efficient degradation of toxic organic pollutants with Ni2O3/Ti2-xBx under
Visible irradiation.J.Am.Chem.Soc.2004,126,4782-4783.).Nevertheless, TiO2Photochemical catalyst
Application there are still two big key technical problems: 1. TiO2Greater band gap can only utilize ultraviolet light portion a small amount of in sunlight
Point, optical response range is relatively narrow；2. the electron-hole pair stability of generation is poor, is easy to happen phase body after the excitation of photochemical catalyst light
Inside and outside is compound, photon utilization rate it is low (Zhao Huan, the preparation of mesoporous TiO2 composite photo-catalyst and photocatalytic degradation of dye waste water
Research, Chang An University, 2013).ZnO has and TiO2Similar forbidden bandwidth, while again with low in cost, preparation process is simple
It is single, nontoxic, pollution-free, the advantages that degradation efficiency is higher, become the suitable selection of extensive treatment of Organic Wastewater, but ZnO only inhales
Ultraviolet light is received, and under ultraviolet light, photoetch can occur for ZnO, can dissolve again under extreme pH value, photocatalytic
It can largely be influenced again by factors such as material this body structure, particle size, pattern, defect kind and concentration, and
These factors are further influenced by material preparation method, and (Li Meng, the preparation of different-shape ZnO material and photocatalysis performance are ground
Study carefully, He'nan Normal University, 2013；Zhou Mojiao, the controlledly synthesis and its Photocatalytic Performance Study of zinc oxide base nano composite material,
Zhejiang Normal University, 2013), therefore, ZnO using also restrained.
As shown in the above, various high-level oxidation technologies have respective advantage, also there is respective limitation, therefore,
Scientists are still untiringly opening up thinking, the new high-level oxidation technology of research and development.Mn oxide has excellent catalysis
Activity, and have the advantages that raw material sources are wide, processing technology is simple, production cost is low etc., field, which is administered, in waste water from dyestuff sends out
The effect of waving.Mn oxide can not only be used to handle a variety of dye wastewater with high concentration, but also processing method has without illumination, nothing
It i.e. implementable under secondary pollution, room temperature, many advantages, such as percent of decolourization is high, COD removal rate is high, therefore, is handled using Mn oxide
Waste water from dyestuff receives significant attention that (Wang Zheng, Mn oxide study the absorption of methylene blue dyestuff and oxidative decoloration, Chinese Sea
University, 2007；Li Hongyan, mesoporous and hollow structure Mn oxide preparation and its catalytic performance research, HeFei University of Technology,
2010).Although as described above, Mn oxide catalytic oxidant oxygenolysis dye field have price advantage outstanding,
Mn oxide obtained is mostly powdered or graininess at present, after catalytic oxidant oxygenolysis dyestuff, easily remains on water body
In, it need to be separated by means such as filtering, centrifugations, improve application cost again, limit its application.Therefore, it researches and develops
The Mn oxide base catalysis material that can directly 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, and poly- (methyl) acrylate hydrolyzes in water soluble alkali solution, forms and receive base rich in carboxylic acid
Poly- (methyl) acrylate of group, carboxylic acid receive the presence of group, make the dyestuff water body containing composite hollow fibre in alkalinity, alkaline item
Hydrogen peroxide decomposition rate is dramatically speeded up under part, and the hydrogen peroxide for participating in generating active oxygen species (such as hydroxyl radical free radical) subtracts
It is few, under comprehensive function, composite hollow fibre is caused to be difficult to reuse.Therefore, to further decrease application cost, improve compound
Doughnut reusability is imperative.
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 doughnut in inorganic acid aqueous solution
It is hydrolyzed, it is and then above-mentioned hollow with neutral potassium permanganate solution processing after being washed repeatedly through deionized water, being dry
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 routine
Mn oxide, hydroxyl are oxidized and generate carboxylic acid group, between conventional Mn oxide and carboxylic acid group under strong complexing, are made with poly-
(methyl) acrylate is skeleton, and conventional Mn oxide is the composite hollow fibre of loaded article.Hydrolysis under acid condition will be big
Quantity carboxylic acid's base assigns doughnut, on the one hand from outward appearance to inner essence improves the ability of the affine potassium permanganate solution of doughnut, is
Subsequent potassium permanganate solution processing provides convenience, while can be obviously improved the ability of doughnut complexing Mn oxide, for suppression
Falling off for Mn oxide processed provides safeguard；On the other hand acid pH is provided for subsequent potassium permanganate processing and final application
Environment, acidic pH environment are remarkably improved the oxidisability of potassium permanganate, make its redox reaction between hydroxyl be easier to occur,
It is more thorough, in addition, the decomposition of hydrogen peroxide can be effectively suppressed in acidic pH environment, more hydrogen peroxide is made to participate in generating activity
Oxygen species (such as hydroxyl radical free radical) can effectively promote the removal rate of dyestuff, shorten catalysis time.Neutral potassium permanganate solution
Processing makes doughnut load conventional Mn oxide again.In this case, cause multiple obtained by patent 201610343408.8
Close doughnut reusability difference factor all avoided, therefore, by manufacturing method of the present invention obtain it is compound in
Hollow fiber has fabulous reusability, and application cost significantly reduces, and more meets the requirement of industrial applicibility.
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 rouge；
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, acrylic acid just ester, 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 condition
Lower deaeration, time are 0~60min, quantify mixed solution by peristaltic pump and are transported in spinning pack, after spinneret orifice squeezes out
Hollow dynamic analysis of spinning is formed, hollow dynamic analysis of spinning outer surface is contacted with the coagulator in coagulating bath, in addition, will coagulate by peristaltic pump
Gu agent is quantitatively transported to inside hollow dynamic analysis of spinning, contact it with hollow dynamic analysis of spinning inner surface, coagulator is by deionized water
It being formed with organic solvent, the mass ratio of deionized water and organic solvent is 10: 0~5: 5, under double diffusion effect, hollow spinning
Silk thread is cured as doughnut, doughnut washed once above in deionized water, is placed in air dry oven, In
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) acidic hydrolysis technique: taking doughnut made from above-mentioned steps (2), place it in fill inorganic acid and go from
In the treatment trough of sub- water, wherein the volume ratio of inorganic acid and deionized water is 0.5: 9.5~9.5: 0.5, and doughnut and liquid
The mass ratio of body is 1: 1~1: 1000, and fluid temperature is 20~95 DEG C in treatment trough, and 30s~12h is handled under earthquake, with
After sufficiently washed, and it is dry；
The inorganic acid is one of the concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid；
(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 20~95 DEG C in treatment trough, and the processing time is 30s~8h, and after treatment takes out hollow fibre
Dimension, is washed, up to cleaning solution, there is no colors, and then doughnut is placed in vacuum drier in 25 repeatedly with deionized water
Dry 1~6h, is made hollow fiber out-phase embryonic stem-like cells catalyst under the conditions of~50 DEG C.
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 in preparation method novel aspects；Finally, being retrieved in addition to this seminar research achievement in applicant
In the range of there is not yet using technique of the present invention manufacture hollow fiber out-phase embryonic stem-like cells catalyst correlation
Document report.
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 acidic 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 makes the ratio between gross mass of monomer 2 and two parts of monomers 1 be 0.01: 9.99~9.99: 0.01. and pour into monomer 2 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 condition
Lower deaeration, time are 0~60min, quantify mixed solution by peristaltic pump and are transported in spinning pack, after spinneret orifice squeezes out
Hollow dynamic analysis of spinning is formed, hollow dynamic analysis of spinning outer surface is contacted with the coagulator in coagulating bath, in addition, will coagulate by peristaltic pump
Gu agent is quantitatively transported to inside hollow dynamic analysis of spinning, contact it with hollow dynamic analysis of spinning inner surface, coagulator is by deionized water
It being formed with organic solvent, the mass ratio of deionized water and organic solvent is 10: 0~5: 5, under double diffusion effect, hollow spinning
Silk thread is cured as doughnut, doughnut washed once above in deionized water, is placed in air dry oven, In
Dry 1~6h under the conditions of 25~50 DEG C, is made nascent doughnut；
(3) acidic hydrolysis technique: taking doughnut made from above-mentioned steps (2), place it in fill inorganic acid and go from
In the treatment trough of sub- water, wherein the volume ratio of inorganic acid and deionized water is 0.5: 9.5~9.5: 0.5, and doughnut and liquid
The mass ratio of body is 1: 1~1: 1000, and fluid temperature is 20~95 DEG C in treatment trough, and 30s~12h is handled under earthquake, with
After sufficiently washed, and it is dry；
(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 20~95 DEG C in treatment trough, and the processing time is 30s~8h, and after treatment takes out hollow fibre
Dimension, is washed, up to cleaning solution, there is no colors, and then doughnut is placed in vacuum drier in 25 repeatedly with deionized water
Dry 1~6h, is made hollow fiber out-phase embryonic stem-like cells catalyst under the conditions of~50 DEG C.
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, the reason is as follows that: with acrylic acid hydroxyl second
Ester, hydroxy propyl methacrylate, hydroxypropyl acrylate are compared, and hydroxyethyl methacrylate is nontoxic chemical reagent, will not be to people
Body generates harm.
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, methacrylic acid just ester, 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 acid solution to doughnut from outward appearance to inner essence, introduces more carboxylics
Acidic group strengthens the ability of doughnut complexing Mn oxide.The preferred methacrylic acid of monomer 2 described in manufacturing method of the present invention is just
Butyl ester, the reason is as follows that: 1. compared with methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid
N-butyl is easier to be copolymerized with monomer 2, and smell is smaller, and reaction condition is milder, and easily controllable polymerization process is not present
Implode, it is highly exothermic phenomena such as；2. with Isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, first
Base n-octyl, isooctyl methacrylate, isodecyl methacrylate, lauryl methacrylate, methacrylic acid
14 esters, hexadecyl metrhacrylate, octadecyl methacrylate ester are compared, and n-BMA side chain lengths are suitable,
It can assign polymer moderate glass transition temperature after polymerization, make it have excellent flexibility, suitable elastic, more prominent
Intensity.
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 acid solution to doughnut from outward appearance to inner essence, draws
Enter more carboxylic acid groups, strengthens the ability of doughnut complexing Mn oxide.Monomer 3 preferably third described in manufacturing method of the present invention
Olefin(e) acid N-butyl, the reason is as follows that: 1. compared with methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate is generated
Polymer have preferable flexibility and lower temperature resistance, be more advantageous to improve doughnut mechanical property and lower temperature resistance
Energy；2. the polymer strands that n-butyl acrylate generates are best, favorably compared with isobutyl acrylate, tert-butyl acrylate
In spinning technique；3. with the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, n-octyl, Isooctyl acrylate monomer, propylene
Sour isodecyl ester, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate long alkyl chain ester are compared, and third
Olefin(e) acid N-butyl is short alkyl chain ester, and when long alkyl chain polyisocyanate polyaddition, since glass transition temperature is extremely low, the polymer of generation is special
Soft not viscous, the later period easily glues each other and at bulk in the reaction, or even leads to the failure of polymerization because moment, implode was agglomerating, and
The above problem is then not present when polymerizeing in 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.
Inorganic acid described in manufacturing method of the present invention is one of the concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid.It is related to
Inorganic acid there is certain risk, but concentrated nitric acid is met light and is easily decomposed, concentrated hydrochloric acid highly volatile, and concentrated phosphoric acid is easy in air
It deliquesces, heats easy dehydration and be changed into pyrophosphoric acid or metaphosphoric acid, and the concentrated sulfuric acid is relatively stable, when being post-processed to doughnut
In the process, it is not likely to produce strong pungent smell, therefore the preferred concentrated sulfuric acid of inorganic acid described in manufacturing method of the present invention.
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.
Embodiment 1
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.
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 dyestuff is 39% when 90min；Above-mentioned as-spun fibre 0.0278g is taken, being put into 10ml concentration is 20mg/L
Cationic blue aqueous solution in, 500ul hydrogen peroxide is added, the removal rate only up to 19.5% of cationic blue dyestuff when 90min.
Embodiment 2
The present embodiment polymerisation in solution and wet spinning technology process and parameter are same as Example 1, and then gained is come into being
Fiber is handled according to following technique, is measured the 60ml concentrated sulfuric acid, then measure 140ml deionized water and be diluted, is then weighed
100g acid solution, is placed in treatment trough, while weighing 10g as-spun fibre, and be immersed in acid solution, at 85 DEG C,
Carry out for when 6h hydrolysis process, sufficiently washed, and be dried in 40 DEG C of vacuum drier after to be processed, obtained
Hydrolyze doughnut.
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 dyestuff is 39% when 90min；Above-mentioned hydrolysis doughnut 0.0278g is taken, being put into 10ml concentration is
In the cationic blue aqueous solution of 20mg/L, 500ul hydrogen peroxide is added, the removal rate of cationic blue dyestuff is only up to when 90min
34.7%.
Embodiment 3
The present embodiment polymerisation in solution, wet spinning and acidic hydrolysis technical process and parameter are same as Example 2, then
Gained hydrolysis doughnut is further processed according to following technique, that is, weighs 3.95g potassium permanganate, placing it in specification is
In the volumetric flask of 250ml, then to deionized water is added in above-mentioned volumetric flask, configuration concentration is the potassium permanganate water of 0.1mol/L
Solution measures the above-mentioned potassium permanganate solution of 90ml, places it in another treatment trough, 10g hydrolysis doughnut is weighed, by it
It is put into treatment trough, is immersed in potassium permanganate solution, 5.5h is handled at 85 DEG C, after the completion clean fiber to cleaning solution
It is then dry in 40 DEG C of vacuum drier until colourless, hollow fiber out-phase embryonic stem-like cells catalyst is made.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g, be put into 10ml concentration be 20mg/L cationic blue aqueous solution in, be added 500ul hydrogen peroxide, carry out for when 90min
Catalysis oxidation resolution process, the removal rate of dyestuff is up to 96.9% when 10min.
Embodiment 4
The present embodiment technical process and parameter are same as Example 3, only by the acidic hydrolysis process concentrated sulfuric acid in embodiment 3 with
Deionized water volume ratio is adjusted to 1: 9 by 3: 7.
Taking 10ml concentration is 20mg/L cationic blue aqueous solution, and 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The removal rate of cationic blue dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 91.1%.
Embodiment 5
The present embodiment technical process and parameter are same as Example 3, only by the acidic hydrolysis process concentrated sulfuric acid in embodiment 3 with
Deionized water volume ratio is adjusted to 2: 8 by 3: 7.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 93.6%.
Embodiment 6
The present embodiment technical process and parameter are same as Example 3, only by the acidic hydrolysis process concentrated sulfuric acid in embodiment 3 with
Deionized water volume ratio is adjusted to 4: 6 by 3: 7.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 93.8%.
Embodiment 7
It is learnt by 3,4,5,6 test result of embodiment, for being 1: 9,2: 8,3 in the concentrated sulfuric acid and deionized water volume ratio:
7,4: 6 when gained hollow fiber out-phase embryonic stem-like cells catalyst for, when the concentrated sulfuric acid and deionized water volume ratio are 3: 7
Gained catalyst is best to dyestuff removal effect, therefore, the concentrated sulfuric acid and deionized water volume in the present embodiment and subsequent embodiment
Than being subject to 3: 7 described in embodiment 3, the present embodiment technical process and parameter are same as Example 3, only at acidic hydrolysis
The reason time becomes 0.5h from 6h in embodiment 3.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 92.8%.
Embodiment 8
The present embodiment technical process and parameter are same as Example 3, and only the acidic hydrolysis processing time is become by 6h in embodiment 3
For 1h.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 93.8%.
Embodiment 9
The present embodiment technical process and parameter are same as Example 3, and only the acidic hydrolysis processing time is become by 6h in embodiment 3
For 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,
The removal rate of cationic blue dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 93.3%.
Embodiment 10
The present embodiment technical process and parameter are same as Example 3, and only the acidic hydrolysis processing time is become by 6h in embodiment 3
For 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,
The removal rate of cationic blue dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 96.0%.
Embodiment 11
The present embodiment technical process and parameter are same as Example 3, and only the acidic hydrolysis processing time is become by 6h in embodiment 3
For 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,
The removal rate of cationic blue dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 93.6%.
Embodiment 12
Learnt by 3,7,8,9,10,11 test result of embodiment, under acidic hydrolysis time different condition gained in
For hollow fiber shape out-phase embryonic stem-like cells catalyst, gained catalyst is to dyestuff removal effect when the acidic hydrolysis time is 6h
Most preferably, therefore, the acidic hydrolysis time is subject to 6h described in embodiment 3 in the present embodiment and subsequent embodiment, the present embodiment
Technical process and parameter are same as Example 3, only by the neutral potassium permanganate oxidation reduction treatment time by the 5.5h in embodiment 3
Become 1h.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 90.7%.
Embodiment 13
The present embodiment technical process and parameter are same as Example 3, only by the neutral potassium permanganate oxidation reduction treatment time
3h is become from the 5.5h in embodiment 3.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 96.1%.
Embodiment 14
The present embodiment technical process and parameter are same as Example 3, only by the neutral potassium permanganate oxidation reduction treatment time
6h is become from the 5.5h in embodiment 3.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 90.3%.
Embodiment 15
The present embodiment technical process and parameter are same as Example 3, only by the neutral potassium permanganate oxidation reduction treatment time
8h is become from the 5.5h in embodiment 3.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 88.3%.
Embodiment 16
It is learnt by 3,12,13,14,15 test result of embodiment, for different in the neutral potassium permanganate oxidation recovery time
Under the conditions of gained hollow fiber out-phase embryonic stem-like cells catalyst for, the neutral potassium permanganate oxidation recovery time be 5.5h
When gained catalyst it is best to dyestuff removal effect, therefore, in the present embodiment and subsequent embodiment neutral potassium permanganate oxidation is also
The former time is subject to 5.5h described in embodiment 3, and the technical process and parameter of the present embodiment are same as Example 3, only will in
The concentration of property potassium permanganate becomes 0.01mol/L from the 0.1mol/L in embodiment 3.
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 dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 53.6%.
Embodiment 17
The technical process and parameter of the present embodiment are same as Example 3, only by the concentration of neutral potassium permanganate by embodiment 3
In 0.1mol/L become 0.02mol/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,
The removal rate of cationic blue dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 91.9%.
Embodiment 18
The technical process and parameter of the present embodiment are same as Example 3, only by the concentration of neutral potassium permanganate by embodiment 3
In 0.1mol/L become 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,
The removal rate of cationic blue dyestuff is 39% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g is put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, and 500ul hydrogen peroxide, removal rate in 90min is added
Up to 70.4%.
Embodiment 19
Learnt by 3,16,17,18 test result of embodiment, under neutral potassium permanganate concentration different condition gained in
For hollow fiber shape out-phase embryonic stem-like cells catalyst, gained catalyst is to dye when neutral potassium permanganate concentration is 0.1mol/L
Expect that removal effect is best, therefore, the present embodiment prepares associated hollow threadiness out-phase Fenton-like by technique described in embodiment 3
Catalysts.
Taking 10ml concentration is the cationic blue aqueous solution of 20mg/L, does not add hydrogen peroxide, under the conditions of magnetic agitation,
The removal rate of cationic blue dyestuff is 9% when 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g, be put into 10ml concentration be 20mg/L cationic blue aqueous solution in, do not add hydrogen peroxide, carry out for when 90min dye
Material is handled, and fiber is taken out up to 96.2%, after being rinsed with deionized water, be placed in air blast exsiccator by dyestuff removal rate after 30min
In, at 40 DEG C after dry 1h, puts it into the cationic blue aqueous solution that 10ml concentration is 20mg/L, does not add hydrogen peroxide,
Carry out for when 90min dyestuff processing, removal rate takes out fiber up to 96.4% after 30min, after being rinsed with deionized water,
It is placed in air blast exsiccator, at 40 DEG C after dry 1h, puts it into the cationic blue aqueous solution that 10ml concentration is 20mg/L,
Do not add hydrogen peroxide, carry out for when 90min dyestuff processing, fiber is taken out, is spent up to 96.8% by removal rate after 30min
After ionized water rinses, be placed in air blast exsiccator, at 40 DEG C after dry 1h, put it into sun that 10ml concentration is 20mg/L from
In sub- indigo plant aqueous solution, do not add hydrogen peroxide, carry out for when 90min dyestuff processing, removal rate, will up to 95.7% after 30min
Fiber takes out, and after being rinsed with deionized water, is placed in air blast exsiccator, at 40 DEG C after dry 1h, puts it into 10ml concentration
Not add hydrogen peroxide in the cationic blue aqueous solution of 20mg/L, carry out for when 90min dyestuff processing, removal rate after 30min
Up to 97%, fiber is taken out, after being rinsed with deionized water, is placed in air blast exsiccator, at 40 DEG C after dry 1h, is put
Enter 10ml concentration be 20mg/L cationic blue aqueous solution in, do not add hydrogen peroxide, carry out for when 90min dyestuff processing,
Removal rate takes out fiber up to 96.8% after 30min, after being rinsed with deionized water, is placed in air blast exsiccator, at 40 DEG C
After dry 1h, put it into the cationic blue aqueous solution that 10ml concentration is 20mg/L, do not add hydrogen peroxide, carry out for when
The dyestuff of 90min is handled, and fiber is taken out up to 96.3%, after being rinsed with deionized water, be placed in drum by removal efficiency after 30min
It air-dries in baking oven, at 40 DEG C after dry 1h, puts it into the cationic blue aqueous solution that 10ml concentration is 20mg/L, do not add
Hydrogen peroxide, carry out for when 90min dyestuff processing, fiber is taken out up to 96.7%, uses deionized water by removal rate after 30min
It after flushing, is placed in air blast exsiccator, at 40 DEG C after dry 1h, puts it into the cationic blue water that 10ml concentration is 20mg/L
Solution does not add hydrogen peroxide, carry out for when 90min dyestuff processing, removal rate takes out fiber up to 90.3% when 90min,
It after being rinsed with deionized water, is placed in air blast exsiccator, fiber after dry 1h reuses at 40 DEG C to get the 9th time, and also
It can continue to reuse.
Hollow fiber out-phase embryonic stem-like cells catalyst 0.0278g obtained by the present embodiment is taken, being put into 10ml concentration is
In the cationic blue aqueous solution of 20mg/L, 35ul hydrogen peroxide is added, removal rate is up to 94.6% in 90min；And when hydrogen peroxide adds
When to enter amount be 50ul, removal rate is up to 97.1% in 90min；And when hydrogen peroxide additional amount is 100ul, removal rate in 90min
Up to 97.3%；And when hydrogen peroxide additional amount is 200ul, removal rate is up to 95.4% in 90min；And work as hydrogen peroxide additional amount
When for 500ul, removal rate is up to 97.1% in 90min, it follows that 50ul hydrogen peroxide is enough.Therefore, the present embodiment is taken
Gained hollow fiber out-phase embryonic stem-like cells catalyst 0.0278g is put into the cationic blue water that 10ml concentration is 20mg/L
In solution, 50ul hydrogen peroxide is added, removal rate takes out fiber, being directly placed into 10ml concentration is up to 96.8% in 10min
In the cationic blue aqueous solution of 20mg/L, 50ul hydrogen peroxide is added, removal rate takes out fiber, directly up to 97% in 10min
Be put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, 50ul hydrogen peroxide be added, in 10min removal rate up to 97%,
Fiber is taken out, is directly placed into the cationic blue aqueous solution that 10ml concentration is 20mg/L, 50ul hydrogen peroxide is added, in 10min
Removal rate takes out fiber up to 95.8%, is directly placed into the cationic blue aqueous solution that 10ml concentration is 20mg/L, is added
50ul hydrogen peroxide, removal rate takes out fiber up to 92.5% in 10min, be directly placed into sun that 10ml concentration is 20mg/L from
In sub- indigo plant aqueous solution, 50ul hydrogen peroxide is added, fiber is taken out up to 92.9%, it is dense to be directly placed into 10ml by removal rate in 10min
Degree is that 50ul hydrogen peroxide is added in the cationic blue aqueous solution of 20mg/L, and removal rate takes fiber up to 84.7% in 10min
Out, it is directly placed into the cationic blue aqueous solution that 10ml concentration is 20mg/L, 50ul hydrogen peroxide is added, removal rate can in 10min
Up to 75.1%, fiber is taken out, is directly placed into the cationic blue aqueous solution that 10ml concentration is 20mg/L, 50ul dioxygen is added
Water, removal rate is up to 70.2% in 10min；Fiber is taken out, it is water-soluble to be directly placed into the cationic blue that 10ml concentration is 20mg/L
In liquid, 50ul hydrogen peroxide is added, fiber is taken out up to 62%, after being rinsed with deionized water, be placed in drum by removal rate in 10min
It air-dries in baking oven, fiber after dry 1h reuses at 40 DEG C to get the 10th time, and can also continue to reuse.
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 dyestuff is 39% after 90min；Take above-mentioned hollow fiber out-phase embryonic stem-like cells catalyst
0.0278g, be put into 10ml concentration be 20mg/L cationic blue aqueous solution in, be added 500ul hydrogen peroxide, carry out for when 90min
Dyestuff processing, removal rate is up to 96.9% when 10min, until 90min removal rate is up to 97.1%, fiber is taken out, is spent
After ionized water rinses, be placed in air blast exsiccator, at 40 DEG C after dry 1h, put it into sun that 10ml concentration is 20mg/L from
In sub- indigo plant aqueous solution, 500ul hydrogen peroxide is added, carry out for when 90min dyestuff processing, when 12min removal rate up to 95.7%,
Until 90min removal rate is up to 96.9%, fiber is taken out, after being rinsed with deionized water, is placed in air blast exsiccator, at 40 DEG C
After lower dry 1h, put it into 10ml concentration be 20mg/L cationic blue aqueous solution in, be added 500ul hydrogen peroxide, carry out for
When 90min dyestuff processing, removal rate is up to 82.3% when 20min, and until 90min removal rate is up to 85.7%, fiber is taken
Out, it after being rinsed with deionized water, is placed in air blast exsiccator, at 40 DEG C after dry 1h, putting it into 10ml concentration is 20mg/
In the cationic blue aqueous solution of L, be added 500ul hydrogen peroxide, carry out for when 90min dyestuff processing, until 90min removal rate can
Up to 66.7%, fiber is taken out, after being rinsed with deionized water, is placed in air blast exsiccator, at 40 DEG C after dry 1h, is put
Enter 10ml concentration be 20mg/L cationic blue aqueous solution in, be added 500ul hydrogen peroxide, carry out for when 90min dyestuff processing,
Until 90min removal rate is up to 41.6%, fiber is taken out, after being rinsed with deionized water, is placed in air blast exsiccator, at 40 DEG C
Fiber after lower dry 1h reuses to get the 5th, and can also continue to reuse.
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, does not add hydrogen peroxide, under the conditions of magnetic agitation,
The removal rate of cationic blue dyestuff is 9% when 90min；Above-mentioned hollow fiber embryonic stem-like cells catalyst 0.1g is taken, is put into
10ml concentration be 20mg/L cationic blue aqueous solution in, do not add hydrogen peroxide, carry out for when 90min dyestuff processing, 90min
When dyestuff removal rate be only 68.0%, and dyestuff removal rate when 19 gained sample of embodiment reuses 9 times in this case
Still up to 90.3%.
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 dyestuff is 39% when 90min；The above-mentioned hollow fiber 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, when 90min
Cationic blue removal rate takes out fiber up to 94.5%, after being rinsed with deionized water, is placed in air dry oven, at 40 DEG C
Under the conditions of after dry 1h, put it into the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide, In be added
Under the conditions of magnetic agitation, the removal rate of cationic blue takes out fiber up to 79.3% when 90min, after being rinsed with deionized water,
It is placed in air dry oven, under the conditions of 40 DEG C after dry 1h, it is water-soluble to put it into the cationic blue that 10ml concentration is 20mg/L
In liquid, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, the removal rate of cationic blue is up to 57.2% when 90min, by fiber
It takes out, after being rinsed with deionized water, is placed in air dry oven, under the conditions of 40 DEG C after dry 1h, put it into 10ml concentration
For in the cationic blue aqueous solution of 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, cationic blue when 90min
Removal rate is only capable of repeating to make under the above conditions close to 39%, i.e. hollow fiber embryonic stem-like cells catalyst obtained by comparative example
With 3 times, and 19 gained sample of embodiment then can be reused at least 5 times in this case.
Claims (4)
1. a kind of preparation 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
State monomer 1 be one of hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate,
The monomer 2 is methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, methyl
Isobutyl acrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, methacrylic acid are different
Monooctyl ester, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, methyl
One of octadecyl acrylate, the monomer 3 are methyl acrylate, ethyl acrylate, the positive fourth of propyl acrylate, acrylic acid
Ester, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, n-octyl, propylene
The different monooctyl ester of acid, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, in octadecyl acrylate
One kind, the organic solvent are dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, toluene, dimethylbenzene, tetrachloro-ethylene
One of；
(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) acidic hydrolysis technique: doughnut made from above-mentioned steps (2) is taken, places it in and fills inorganic acid and deionized water
Treatment trough in, wherein the volume ratio of inorganic acid and deionized water is 0.5: 9.5~9.5: 0.5, and doughnut and liquid
Mass ratio is 1: 1~1: 1000, and fluid temperature is 20~95 DEG C in treatment trough, 30s~12h is handled under earthquake, with laggard
Row sufficiently washing, and it is dry；
(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 20~95 DEG C in treatment trough, and the processing time is 30s~8h, after treatment, taking-up doughnut,
It is washed repeatedly with deionized water, up to cleaning solution, there is no colors, then doughnut is placed in vacuum drier in 25~
Dry 1~6h, is made hollow fiber out-phase embryonic stem-like cells catalyst under the conditions of 50 DEG C.
2. a kind of preparation 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 preparation method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, special
Sign is that the inorganic acid is one of the concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid.
4. a kind of system of hollow fiber out-phase embryonic stem-like cells catalyst described in any one of claim 1 to 3
Preparation 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 inorganic acid are the concentrated sulfuric acid.
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