CN107308988A - A kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst - Google Patents
A kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst Download PDFInfo
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- CN107308988A CN107308988A CN201710531539.3A CN201710531539A CN107308988A CN 107308988 A CN107308988 A CN 107308988A CN 201710531539 A CN201710531539 A CN 201710531539A CN 107308988 A CN107308988 A CN 107308988A
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- monomer
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- acrylate
- embryonic stem
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 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
- 230000003287 optical effect Effects 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
- 239000002957 persistent organic pollutant Substances 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
- 238000001556 precipitation Methods 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
- 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
- 239000003643 water by type 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)
- Water Supply & Treatment (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses the design of complex fiber material in textile material field and manufacture, 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) is quick, efficient oxidation decomposes a variety of dyestuffs composite hollow fibre manufacture method.The manufacture method has used a series of technologies such as acidic hydrolysis, neutral potassium permanganate oxidation reduction treatment on the basis of fibre-forming polymer structure design, synthesis and spinning technique, mainly.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 decay of dyestuff clearance are small, time needed for reaching certain clearance 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 manufacture, it is related to a kind of hollow fiber different
The preparation of phase Fenton-like catalysts, specially one kind can catalytic oxidants (such as hydrogen peroxide, ozone, persulfate)
Quickly, efficient oxidation decomposes the manufacture method of the composite hollow fibre of a variety of dyestuffs.The manufacture method is in fibre-forming polymer structure
On the basis of design, synthesis and spinning technique, acidic hydrolysis, neutral potassium permanganate oxidation reduction treatment etc. one has mainly been used to be
Row technology.
Background technology
China is manufacturing industry base important in the world, but the mode of production is based on extensive style at present, and environment situation is very
Sternness, wherein, textile industry occupies very important ground as the strong industry of China in national economy and international trade
Position.According to statistics, it is about 1,600,000,000 tons that China produces 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 intractability of dyeing waste water is also in increase.Dyeing waste water has water
The features such as amount is big, organic pollution content is high, colourity is deep, alkalescence 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 into 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 colourity are higher, Er Qie great
Most difficult for biological degradation, also containing a variety of with bio-toxicity or with carcinogenic, teratogenesis and mutagenic organic matter, therefore,
Treatment of dyeing wastewater causes global highest attention.
Generally, being commercially used for handling the method for dyeing waste water has：Physical chemistry (such as adsorb, flocculate) and biology side
Method, wherein, physico-chemical process has the advantages that equipment is simple, easy to operate, but such method is typically that dyestuff etc. is organic
Thing is transferred to solid phase (such as active carbon adsorption) from liquid phase, organic pollution is not completely eliminated, and can bring substantial amounts of solid
, therefore, there is certain defect in terms of removal effect and secondary pollution in body discarded object and regenerative wastewater.Biochemical method
Equipment is simple and convenient to operate, operating cost is low, but long processing period, hold facility area are big, can be because of organic contaminations such as dyestuffs
Thing can not be effective to biological toxic action removal, be also possible to generate carcinogenic aromatic amine chemical combination under conditions of anaerobism
Thing.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 dye molecule is resolved into the mankind and environmentally friendly small-molecule substance (such as water
With carbon dioxide etc.), and have the advantages that the reaction time is short, treatment effeciency is high, product does not result in secondary pollution, it is therefore, high
Level oxidation technology increasingly causes the concern of people.
High-level oxidation technology generally has：Ozonation, Fenton reagent oxidizing process, photochemical oxidation method, photochemical catalytic oxidation
Method etc..
Ozonation is, using ozone as oxidant, the oxygen to organic pollutions such as dyestuffs can instantaneously to be completed at low concentrations
Change degraded, non-secondary pollution, but have that ozone generating apparatus is expensive, cost for wastewater treatment is high, be not suitable for big flow waste water
The shortcomings of processing.Fenton reagent oxidizing process uses Fe2+(Fe3+)/H2O2As catalytic oxidation system, its 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 pollution, 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)3Precipitation, causes reaction efficiency to reduce, and contains relatively large Fe in water2+(Fe3+), secondary dirt can be caused
Dye.Photochemical oxidation method frequently with oxidation system be H2O2/UV、O3/UV、H2O2/O3/ UV etc., is a kind of light without catalyst
Chemical reaction, the technology have the advantages that easy to operate, non-secondary pollution, can permineralization organic matter etc. it is prominent, but there is also anti-
The shortcomings of long, costly between seasonable.Photocatalytic oxidation inherits the advantage of photochemical oxidation method, while catalyst is introduced again,
Reaction efficiency is greatly accelerated, particularly with TiO2As the research of photochemical catalyst by (Asahi, the R. of attracting attention extensively；
Morikawa, T.；Ohwaki.T.Visible-light photocatalysis in nitrogen doped titanium
Oxides.Science, 2001,193,269-271；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 still suffer from two big key technical barriers：①TiO2Greater band gap, can only utilize ultraviolet light portion a small amount of in sunshine
Point, photoresponse scope is narrower；2. after photochemical catalyst light is excited, the electron-hole pair stability of generation is poor, easily occurs phase body
It is inside and outside compound, photon utilization rate it is low (Zhao Huan, the preparations of mesoporous TiO2 composite photo-catalysts and photocatalytic degradation of dye waste water
Research, Chang An University, 2013).ZnO has and TiO2Similar energy gap, while having with low cost, preparation technology simple again
It is single, nontoxic, pollution-free, the advantages of degradation efficiency is higher, as the appropriately selected 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 under extreme pH value, its photocatalytic
Largely it can be influenceed again by factors such as material this body structure, particle size, pattern, defect kind and concentration, and
These factors are further influenceed 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 of zinc oxide base nano composite and its Photocatalytic Performance Study,
Zhejiang Normal University, 2013), therefore, ZnO application is 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, with excellent catalysis
Activity, and with raw material sources are wide, processing technology is simple, the low advantage of production cost, it administers field hair in waste water from dyestuff
The effect of waving.Mn oxide not only can be for handling a variety of dye wastewater with high concentration, and processing method has without illumination, nothing
It can implement under secondary pollution, normal temperature, many advantages, such as percent of decolourization is high, COD clearances are high, therefore, be handled using Mn oxide
Waste water from dyestuff receives significant attention (Wang Zheng, absorption and oxidative decoloration research of the Mn oxide to methylene blue dyestuff, Chinese Sea
University, 2007；Li Hongyan, mesoporous and hollow-core construction Mn oxide preparation and its catalytic performance research, HeFei University of Technology,
2010).Although as described above, Mn oxide has prominent price advantage in catalytic oxidant oxidation Decomposition dye field,
Obtained Mn oxide is generally powdered or graininess at present, after catalytic oxidant oxidation Decomposition dyestuff, easily residues in water body
In, it need to be separated by means such as filtering, centrifugations, application cost is improved again, limit its application.Therefore, research and develop
The Mn oxide base catalysis material that directly can be separated with water body has important practical significance.
Based on above-mentioned background, this seminar is synthesized using (methyl) esters of acrylic acid material 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 method
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 alkali lye etching from outward appearance to inner essence and hydroxyl and potassium permanganate in potassium permanganate mixed solution
Should, potassium permanganate is reduced and generates Mn oxide, and hydroxyl is oxidized and generates carboxylic acid group, is deposited between Mn oxide and carboxylic acid group
In strong complexing, the Mn oxide of generation is not only securely joined with fiber surfaces externally and internally, but also be carried on interior
In hole between outer surface, it is made using poly- (methyl) acrylate as skeleton, Mn oxide is fine for the composite hollow of loaded article
Dimension, composite hollow fibre not only has the characteristic of catalytic oxidant oxidation Decomposition dyestuff, and directly can divide during application with water body
From its specific surface area is also very big, therefore high with catalytic activity, the advantages of processing speed is fast, dyestuff clearance is high, with the above
For inventive point, this seminar has applied for Chinese invention patent (application number：CN201610343408.8).Follow-up study discovery, on
State composite hollow fibre poor in the presence of significant defect, i.e. a reusability in application process, with the increase of access times,
Composite hollow fibre catalytic activity drastically declines, and dyestuff clearance sharp-decay, the time needed for reaching certain clearance is very big
Increase, is then studied its reusability variation reason, as a result finds 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 other from
Son is exchanged, in application process, and different kinds of ions generation is decomposed with dye oxidation, and then is exchanged 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 is hydrolyzed in water soluble alkali solution, forms and receive base rich in carboxylic acid
Poly- (methyl) acrylate of group, carboxylic acid receives the presence of group, makes the dyestuff water body containing composite hollow fibre in alkalescence, alkaline bar
Hydrogen peroxide decomposition rate is dramatically speeded up under part, and the hydrogen peroxide for participating in generation active oxygen species (such as hydroxyl radical free radical) subtracts
It is few, under comprehensive function, cause composite hollow fibre to be difficult to reuse.Therefore, it is further reduction application cost, improves compound
Doughnut reusability is imperative.
The content of the invention
For the deficiency of the existing technology of patent 201610343408.8, the technical problem that the present invention is intended to solve is to provide one
Plant the manufacture method of the hollow fiber out-phase embryonic stem-like cells catalyst with fabulous reusability.The manufacture method is first
Suitable monomer is first selected on the basis of prior art invention, the polymer solution rich in hydroxyl is prepared using solution polymerization process,
Using this solution as spinning solution, doughnut is spinned using wet spinning technology, then to doughnut in inorganic acid aqueous solution
Processing is hydrolyzed, it is and then above-mentioned hollow with neutral potassium permanganate solution processing after deionized water cyclic washing, drying
Fiber, makes it occur redox reaction with hydroxyl, due to no longer there is water soluble alkali, potassium permanganate is reduced and generates routine
Mn oxide, hydroxyl is oxidized and generates carboxylic acid group, between conventional Mn oxide and carboxylic acid group under strong complexing, is 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 facility, while the ability that doughnut is complexed Mn oxide can be obviously improved, for suppression
Coming off for Mn oxide processed provides safeguard；On the other hand it is that subsequent potassium permanganate processing and final application provide acid pH
Environment, acidic pH environment is remarkably improved the oxidisability of potassium permanganate, make its redox reaction between hydroxyl be more easy to occur,
It is more thorough, in addition, acidic pH environment can effectively suppress the decomposition of hydrogen peroxide, more hydrogen peroxide is participated in generation activity
Oxygen species (such as hydroxyl radical free radical), can effectively lift the clearance of dyestuff, shorten catalysis time.Neutral potassium permanganate solution
Processing makes doughnut load conventional Mn oxide again.In this case, cause the gained of patent 201610343408.8 multiple
The factor for closing doughnut reusability difference is all avoided, therefore, by being combined that manufacture method of the present invention is obtained
Hollow fiber has fabulous reusability, and application cost is significantly reduced, and more meets the requirement of industrial applicibility.
The technical scheme that the present invention solves the technical problem is：Design a kind of hollow fiber out-phase embryonic stem-like cells
The manufacture method of catalyst, its technical process is as follows：
(1) solution polymerization process：The quality monomers 1 such as two parts are weighed, is placed in suitable beaker a, b, weighs respectively
Monomer 2, it is 0.01: 9.99~9.99: 0.01 to make the ratio between gross mass of monomer 2 and two parts of monomers 1, and monomer 2 is poured into above-mentioned
In beaker a, initiator is weighed, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and will trigger
Agent is added in beaker a, and initiator is weighed again, and current initiator quality is 0.2~2% of the mass of monomer 1 in beaker b, and
Beaker b is added to, magnetic agitation is opened, until initiator is completely dissolved in beaker a, b, solvent is weighed, makes solvent and two parts of lists
The ratio between body 1 and the gross mass of monomer 2 are 1: 5~5: 1, and solvent is added in above-mentioned beaker a, open magnetic agitation, make burning
Material mixing is uniform in cup a, then goes to solution in beaker a in polymeric kettle, is passed through nitrogen empty to be remained in emptying polymeric kettle
Gas, opens polymeric kettle heating system, is warming up to 50~100 DEG C, is now added drop-wise to the monomer 1 containing initiator in beaker b dropwise
In polymeric kettle, time for adding is controlled within 10~60min, after completion of dropwise addition, is continued to react 2~6h, is obtained polymer solution A,
Resulting polymers solution A is transferred in suitable beaker, seals standby, change above-mentioned monomer 2 into monomer 3, performed above-mentioned poly-
Conjunction program, obtains polymer solution B, resulting polymers solution B is transferred in suitable beaker, and seals standby；
The monomer 1 is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, acrylic acid hydroxypropyl
One kind in fat；
The monomer 2 be methyl methacrylate, EMA, 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 kind in 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 kind in sour isodecyl ester, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate；
The initiator be benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, TBHP,
One kind in cumyl peroxide, di-t-butyl peroxide；
The solvent is in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene
One kind；
(2) wet spinning technology：By above-mentioned steps (1) resulting polymers solution A, B using volume ratio as 99.99: 0.01~
Mixed at 0.01: 99.99, and by mixture 0.5~3h of magnetic agitation, to be well mixed, gained mixed solution is poured into
Wet spinning is contained in liquid device, will then be contained liquid device and is placed in vacuum drier in 25~95 DEG C and -0.07~-0.1MPa conditions
Lower deaeration, the time is 0~60min, quantifies mixed solution by peristaltic pump and is transported in spinning pack, after being extruded through spinneret orifice
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 be solidifying by peristaltic pump
Gu agent is quantitatively transported to inside hollow dynamic analysis of spinning, it is set to be contacted with hollow dynamic analysis of spinning inner surface, coagulator is by deionized water
With solvent composition, the mass ratio of deionized water and solvent is 10: 0~5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is consolidated
Doughnut is turned to, doughnut be washed once into the above in deionized water, is placed in air dry oven, at 25~50 DEG C
Under the conditions of dry 1~6h, nascent doughnut is made；
The solvent is in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene
One kind；
(3) acidic hydrolysis technique：Doughnut made from taking above-mentioned steps (2), be placed on 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 fully washed, and dry；
The inorganic acid is one kind in 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 on
In, certain volume deionized water is added, configuration concentration is 0.0001~0.3mol/L potassium permanganate solution, measures certain body
The above-mentioned potassium permanganate solution of product, and be placed in treatment trough, doughnut is placed in place after being hydrolyzed obtained by above-mentioned steps (3)
Manage in groove, and be immersed in potassium permanganate solution, doughnut is 1: 1 with potassium permanganate solution mass ratio in treatment trough
~1: 1000, fluid temperature is 20~95 DEG C in treatment trough, and processing time is 30s~8h, after processing terminates, and takes out hollow fibre
Dimension, uses deionized water cyclic washing, until doughnut, there is no color, is then placed in vacuum drier in 25 by cleaning solution
1~6h is dried under the conditions of~50 DEG C, hollow fiber out-phase embryonic stem-like cells catalyst is made.
Compared with prior art products, the present invention obtained by using poly- (methyl) acrylate as skeleton, Mn oxide is negative
The composite hollow fibre of loading morphologically has outstanding advantage, and Mn oxide common at present is generally powdered or graininess,
After catalytic oxidant oxidation Decomposition dyestuff, these Mn oxides are easily residued in water body, need to be by means point such as filtering, centrifugations
From for nanoscale manganese oxide catalyst, being also difficult to thoroughly remove from water body even with means such as filtering, centrifugations, pole
Secondary pollution is easily caused to water body, and can be taken out after present invention gained composite hollow fibre use directly from water, at drying
Manage or without drying process, can repeatedly utilize, significantly reduce the risk factor that processing cost and processing are brought in itself, and can profit
Variform product is processed into weaving or non-woven means, demand of the different application field to form, Jin Erkuo can be met
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 oxidation Decomposition dyestuff is significantly improved, in addition, can be direct
Carry waste water from dyestuff circulation, waste water from dyestuff when inside hollow fibre flow, can a step complete dyestuff catalysis oxidation decomposition,
The water body of exit outflow is water purification, and after particularly being handled through pore, composite hollow fibre can do filtering medium and use, in sieve
Divide, be catalyzed the purified treatment completed under double effects to water body, degree of purification is obviously improved；With the institute of patent 201610343408.8
Obtain composite hollow fibre to compare, present invention gained composite hollow fibre can be repeatedly used, and with the increase of access times, it is multiple
Close doughnut catalytic activity and the decay of dyestuff clearance is small, the time needed for reaching certain clearance only has increased slightly, because
This, application cost is more cheap in preparation method novel aspects；Finally, in addition to this seminar achievement in research, in applicant's retrieval
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.
Embodiment
The present invention is further discussed below with reference to example：A kind of hollow fiber out-phase Fenton-like that the present invention is designed is anti-
Answer catalyst manufacture method (hereinafter referred to as manufacture method) 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, the problem of Mn oxide is poor for the composite hollow fibre reusability of loaded article, for dye
Expect that the water body treatings containing organic matter such as waste water create new material, its technical process or step are as follows：
(1) solution polymerization process：The quality monomers 1 such as two parts are weighed, is placed in suitable beaker a, b, weighs respectively
Monomer 2, it is 0.01: 9.99~9.99: 0.01 to make the ratio between gross mass of monomer 2 and two parts of monomers 1, and monomer 2 is poured into above-mentioned
In beaker a, initiator is weighed, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and will trigger
Agent is added in beaker a, and initiator is weighed again, and current initiator quality is 0.2~2% of the mass of monomer 1 in beaker b, and
Beaker b is added to, magnetic agitation is opened, until initiator is completely dissolved in beaker a, b, solvent is weighed, makes solvent and two parts of lists
The ratio between body 1 and the gross mass of monomer 2 are 1: 5~5: 1, and solvent is added in above-mentioned beaker a, open magnetic agitation, make burning
Material mixing is uniform in cup a, then goes to solution in beaker a in polymeric kettle, is passed through nitrogen empty to be remained in emptying polymeric kettle
Gas, opens polymeric kettle heating system, is warming up to 50~100 DEG C, is now added drop-wise to the monomer 1 containing initiator in beaker b dropwise
In polymeric kettle, time for adding is controlled within 10~60min, after completion of dropwise addition, is continued to react 2~6h, is obtained polymer solution A,
Resulting polymers solution A is transferred in suitable beaker, seals standby, change above-mentioned monomer 2 into monomer 3, performed above-mentioned poly-
Conjunction program, obtains polymer solution B, resulting polymers solution B is transferred in suitable beaker, and seals standby；
(2) wet spinning technology：By above-mentioned steps (1) resulting polymers solution A, B using volume ratio as 99.99: 0.01~
Mixed at 0.01: 99.99, and by mixture 0.5~3h of magnetic agitation, to be well mixed, gained mixed solution is poured into
Wet spinning is contained in liquid device, will then be contained liquid device and is placed in vacuum drier in 25~95 DEG C and -0.07~-0.1MPa conditions
Lower deaeration, the time is 0~60min, quantifies mixed solution by peristaltic pump and is transported in spinning pack, after being extruded through spinneret orifice
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 be solidifying by peristaltic pump
Gu agent is quantitatively transported to inside hollow dynamic analysis of spinning, it is set to be contacted with hollow dynamic analysis of spinning inner surface, coagulator is by deionized water
With solvent composition, the mass ratio of deionized water and solvent is 10: 0~5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is consolidated
Doughnut is turned to, doughnut be washed once into the above in deionized water, is placed in air dry oven, at 25~50 DEG C
Under the conditions of dry 1~6h, nascent doughnut is made；
(3) acidic hydrolysis technique：Doughnut made from taking above-mentioned steps (2), be placed on 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 fully washed, and dry；
(4) neutral potassium permanganate oxidation reduction treatment technique：The potassium permanganate of certain mass is weighed, volumetric flask is placed on
In, certain volume deionized water is added, configuration concentration is 0.0001~0.3mol/L potassium permanganate solution, measures certain body
The above-mentioned potassium permanganate solution of product, and be placed in treatment trough, doughnut is placed in place after being hydrolyzed obtained by above-mentioned steps (3)
Manage in groove, and be immersed in potassium permanganate solution, doughnut is 1: 1 with potassium permanganate solution mass ratio in treatment trough
~1: 1000, fluid temperature is 20~95 DEG C in treatment trough, and processing time is 30s~8h, after processing terminates, and takes out hollow fibre
Dimension, uses deionized water cyclic washing, until doughnut, there is no color, is then placed in vacuum drier in 25 by cleaning solution
1~6h is dried under the conditions of~50 DEG C, hollow fiber out-phase embryonic stem-like cells catalyst is made.
Monomer 1 described in manufacture method of the present invention is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate
One kind in propyl ester, hydroxypropyl acrylate.The effect of monomer 1 is as follows：1. hydroxyl is introduced, hydroxyl is as reducing agent, with permanganic acid
Redox reaction occurs for potassium, realizes the in-situ preparation of Mn oxide, and hydroxyl is oxidized to carboxyl, carboxylic under potassium permanganate effect
Base is complexed with generated in-situ Mn oxide, realizes load of the doughnut to Mn oxide；2. the hydrophilic of doughnut is improved
Performance, is easy to the processing of waste water from dyestuff；3. monomer conversion during polymerisation in solution is improved, the polymer molecular weight that narrows is distributed,
Improve the spinning spinnability of polymer.
The preferred hydroxyethyl methacrylate of monomer 1 described in manufacture method of the present invention, reason is as follows：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 produces harm.
Monomer 2 described in manufacture method of the present invention is methyl methacrylate, EMA, 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, EHMA, isodecyl methacrylate, lauryl methacrylate, methacrylic acid 14
One kind in ester, hexadecyl metrhacrylate, octadecyl methacrylate.The effect of monomer 2 is as follows：1. the homopolymer of monomer 2
Solution has preferable spinning spinnability, therefore the introducing of monomer 2 can improve the spinning spinnability of polymer solution, be conducive to wet method
Spinning technique；2. the hydrogen bond action between destruction monomer 1 and solvent, improves rate of polymerization, suppresses the homopolymerization of monomer 1, makes condensate
System's generation copolymer, in last handling process, accelerates hydrolysis of the acid solution to doughnut from outward appearance to inner essence, introduces more carboxylic acids
Base, reinforcing doughnut is complexed the ability of Mn oxide.The positive fourth of preferred methacrylic acid of monomer 2 described in manufacture method of the present invention
Ester, reason is as follows：1. compared with methyl methacrylate, EMA, propyl methacrylate, methacrylic acid is just
Butyl ester is easier to be copolymerized with monomer 2, and smell is smaller, and reaction condition is gentleer, it is easy to control polymerization process, in the absence of quick-fried
The phenomenon such as poly-, highly exothermic；2. with Isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, methyl
N-octyl, EHMA, isodecyl methacrylate, lauryl methacrylate, methacrylic acid ten
Four esters, hexadecyl metrhacrylate, octadecyl methacrylate ester are compared, and n-BMA side chain lengths are suitable, are gathered
It can assign polymer moderate glass transition temperature after conjunction, make it have excellent pliability, suitable elastic, more prominent
Intensity.
Monomer 3 described in manufacture 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
In the different monooctyl ester of olefin(e) acid, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate
One kind.The effect of monomer 3 is as follows：1. the homopolymer of monomer 3 has a fabulous pliability, prominent elasticity, therefore monomer 3 draws
Enter to substantially improve the pliability and elasticity of doughnut, be conducive to the progress of post processing, there is final doughnut
More practical mechanical property；2. the hydrogen bond action between destruction monomer 1 and solvent, improves rate of polymerization, suppresses the equal of monomer 1
It is poly-, polymerization system is generated copolymer, in last handling process, accelerate hydrolysis of the acid solution to doughnut from outward appearance to inner essence, introduce
More carboxylic acid groups, reinforcing doughnut is complexed the ability of Mn oxide.The preferred propylene of monomer 3 described in manufacture method of the present invention
Sour N-butyl, reason is as follows：1. compared with methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate generation
Polymer has preferable pliability and lower temperature resistance, is more beneficial for improving the mechanical property and lower temperature resistance of doughnut
Energy；2. compared with isobutyl acrylate, tert-butyl acrylate, the polymer strands of n-butyl acrylate generation are best, favorably
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, during long alkyl chain polyisocyanate polyaddition, because glass transition temperature is extremely low, and the polymer of generation is special
Not soft viscous, the later stage easily glues and into bulk each other in the reaction, or even causes the failure of polymerization implode is agglomerating because of moment, and
Above mentioned problem is then not present during short alkyl chain ester n-butyl acrylate polymerization polymerization.
Initiator described in manufacture method of the present invention is benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide,
One kind in TBHP, cumyl peroxide, di-t-butyl peroxide.The principle of selection initiator includes：①
Half-life period appropriate initiator is selected according to polymerization temperature, makes polymerization time moderate, from the initiator of high activity, i.e. half-life period
Shorter initiator, to improve rate of polymerization, shortens polymerization time, while can reduce polymerization temperature and reduce initiator amount；
2. it should also be taken into account that initiator polymer quality is whether there is influence, initiator have it is non-toxic, using and storage process in whether pacify
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 TBHP 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 reduction Increased Plasma Half-life, temperature rise 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 suitable, it is ensured that preferable extent of polymerization is reached in the polymerization time being related to, and due to benzoyl peroxide first
Acyl belongs to low toxicity chemicals, uses and store comparatively safe, therefore the preferred benzoyl peroxide first of the initiator described in manufacture method of the present invention
Acyl.
Solvent described in manufacture method of the present invention is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene,
One kind in dimethylbenzene, tetrachloro-ethylene.Compared with dimethyl acetamide, dimethyl sulfoxide (DMSO), the dimethylformamide dissolving present invention
The ability of synthesized polymer is protruded the most, when obtained polymer solution is contacted with water, and dimethylformamide enters water body
Speed is also relatively fast, therefore is more beneficial for dynamic analysis of spinning solidified forming；Compared with toluene, dimethylbenzene, tetrachloro-ethylene, dimethyl methyl
The toxicity of acid amides is minimum, is lower toxicity product, and other solvents are middle high toxicity product, for these reasons, present invention manufacture
The preferred dimethylformamide of solvent described in method.
Inorganic acid described in manufacture method of the present invention is one kind in the concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid.It is related to
Inorganic acid there is certain danger, but concentrated nitric acid is met light and easily decomposed, and concentrated hydrochloric acid highly volatile, concentrated phosphoric acid is easy in atmosphere
Deliquescence, heats easy dehydration and is changed into pyrophosphoric acid or metaphosphoric acid, and the concentrated sulfuric acid is stablized relatively, when being post-processed to doughnut
During, it is not likely to produce strong impulse smell, therefore the preferred concentrated sulfuric acid of inorganic acid described in manufacture method of the present invention.
Specific embodiment is given below, so that the present invention to be described in further detail, but the application claims are not
Limited by specific embodiment.
Embodiment 1
Two parts of 10g hydroxyethyl methacrylates are weighed, is respectively placed in beaker a, b, is weighing 30g methacrylic acids just
Butyl ester, and be poured into above-mentioned beaker a, 0.2g benzoyl peroxides are weighed, and add it in above-mentioned beaker a, weigh
0.05g benzoyl peroxides, are added it in above-mentioned beaker b, open magnetic agitation, until the benzoyl peroxide in beaker a, b
Formyl is completely dissolved, hereafter, weighs 50g dimethylformamides, 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, the sky for being passed through nitrogen to be remained in emptying polymeric kettle
Gas, opens polymeric kettle heating system, is warming up to 85 DEG C, by the hydroxyethyl methacrylate containing initiator in beaker b dropwise now
It is added drop-wise in polymeric kettle, time for adding is 0.5h, after completion of dropwise addition, continues to react 2h, it is after reaction terminates, resulting polymers are molten
Liquid A is moved in suitable beaker, is sealed standby；Above-mentioned n-BMA is replaced with n-butyl acrylate, is repeated above-mentioned
Experiment, after reaction terminates, obtains polymer solution B, is placed in suitable beaker, seals standby；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 well mixed, will be well mixed
Solution pour into wet spinning contain liquid device in, then by contain liquid device be placed in vacuum drier in 40 DEG C and -0.1MPa bars
Deaeration under part, the time is 30min, quantifies mixed solution by peristaltic pump and is transported in spinning pack, and quantitative transporting velocity is
0.6ml/min, forms hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface and the coagulator in coagulating bath after being extruded through spinneret orifice
Contact, in addition, coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump, makes it be connect with hollow dynamic analysis of spinning inner surface
Touch, the speed of conveying coagulator is 0.9ml/min, and coagulator is made up of deionized water, under double diffusion effect, hollow spinning is thin
Stream is cured as doughnut, and doughnut washed once into the above in deionized water, is placed in air dry oven, at 50 DEG C
Under the conditions of dry 1h, nascent doughnut is made.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 90min；Above-mentioned as-spun fibre 0.0278g is taken, 10ml concentration is put into for 20mg/L
The cationic blue aqueous solution in, add 500ul hydrogen peroxide, the clearance of cationic blue dyestuff only up to 19.5% during 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 acids, then is measured 140ml deionized waters and is diluted, and is then weighed
100g acid solutions, are placed in treatment trough, while weighing 10g as-spun fibres, and are immersed in acid solution, at 85 DEG C,
6h hydrolysis process when entering behavior, it is pending fully to be washed afterwards, and be dried in 40 DEG C of vacuum drier, obtain
Hydrolyze doughnut.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 90min；Above-mentioned hydrolysis doughnut 0.0278g is taken, being put into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, 500ul hydrogen peroxide is added, the clearance of cationic blue dyestuff is only up to during 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 handled according to following technique, that is, weighs 3.95g potassium permanganate, being placed on specification is
In 250ml volumetric flask, then to deionized water is added in above-mentioned volumetric flask, configuration concentration is 0.1mol/L potassium permanganate water
Solution, measures the above-mentioned potassium permanganate solutions of 90ml, is placed in another treatment trough, 10g hydrolysis doughnuts is weighed, by it
Be put into treatment trough, be immersed in potassium permanganate solution, 5.5h is handled at 85 DEG C, after the completion of fiber is cleaned to cleaning solution
Untill colourless, then dried in 40 DEG C of vacuum drier, hollow fiber out-phase embryonic stem-like cells catalyst is made.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds 500ul hydrogen peroxide, 90min when entering behavior
Catalysis oxidation resolution process, the clearance of dyestuff is up to 96.9% during 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.
It is the 20mg/L cationic blue aqueous solution to take 10ml concentration, adds 500ul hydrogen peroxide, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
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.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
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.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
Up to 93.8%.
Embodiment 7
Learnt by the test result of embodiment 3,4,5,6, for being 1: 9,2: 8,3 in the concentrated sulfuric acid and deionized water volume ratio:
7th, 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 optimal to dyestuff removal effect, therefore, the concentrated sulfuric acid and deionized water volume in the present embodiment and subsequent embodiment
Than being defined by 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 is changed into 0.5h from 6h in embodiment 3.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
Up to 92.8%.
Embodiment 8
The present embodiment technical process and parameter are same as Example 3, and only acidic hydrolysis processing time 6h in embodiment 3 becomes
For 1h.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
Up to 93.8%.
Embodiment 9
The present embodiment technical process and parameter are same as Example 3, and only acidic hydrolysis processing time 6h in embodiment 3 becomes
For 3h.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
Up to 93.3%.
Embodiment 10
The present embodiment technical process and parameter are same as Example 3, and only acidic hydrolysis processing time 6h in embodiment 3 becomes
For 9h.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
Up to 96.0%.
Embodiment 11
The present embodiment technical process and parameter are same as Example 3, and only acidic hydrolysis processing time 6h in embodiment 3 becomes
For 12h.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
Up to 93.6%.
Embodiment 12
Learnt by the test result of embodiment 3,7,8,9,10,11, in the gained under acidic hydrolysis time different condition
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 defined by 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
It is changed into 1h.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
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 changed into from the 5.5h in embodiment 3.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
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 changed into from the 5.5h in embodiment 3.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
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 changed into from the 5.5h in embodiment 3.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
Up to 88.3%.
Embodiment 16
Learnt by the test result of embodiment 3,12,13,14,15, 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 optimal to dyestuff removal effect, therefore, in the present embodiment and subsequent embodiment neutral potassium permanganate oxidation is also
The former time is defined by 5.5h described in embodiment 3, and the technical process and parameter of the present embodiment are same as Example 3, only by
The concentration of property potassium permanganate is changed into 0.01mol/L from the 0.1mol/L in embodiment 3.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
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 be changed into 0.02mol/L.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
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 be changed into 0.2mol/L.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 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, adds clearance in 500ul hydrogen peroxide, 90min
Up to 70.4%.
Embodiment 19
Learnt by the test result of embodiment 3,16,17,18, in the gained under neutral potassium permanganate concentration different condition
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 optimal, therefore, the present embodiment prepares the fibrous out-phase Fenton-like of associated hollow by technique described in embodiment 3
Catalysts.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, without hydrogen peroxide, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 9% during 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, without hydrogen peroxide, 90min dye when entering behavior
Fiber is taken out up to 96.2%, after deionized water rinsing, is placed in air blast exsiccator by dyestuff clearance after material processing, 30min
In, dry after 1h, put it into the cationic blue aqueous solution that 10ml concentration is 20mg/L at 40 DEG C, without hydrogen peroxide,
Clearance, up to 96.4%, fiber is taken out after 90min dyestuff processing, 30min when entering behavior, after deionized water rinsing,
It is placed in air blast exsiccator, is dried at 40 DEG C after 1h, is put it into the cationic blue aqueous solution that 10ml concentration is 20mg/L,
Without hydrogen peroxide, clearance, up to 96.8%, fiber is taken out, spent after 90min dyestuff processing, 30min when entering behavior
Ionized water rinse after, be placed in air blast exsiccator, at 40 DEG C dry 1h after, put it into 10ml concentration for 20mg/L sun from
In the sub- indigo plant aqueous solution, without hydrogen peroxide, clearance, will up to 95.7% after 90min dyestuff processing, 30min when entering behavior
Fiber takes out, and after deionized water rinsing, is placed in air blast exsiccator, is dried at 40 DEG C after 1h, puts it into 10ml concentration
For in the 20mg/L cationic blue aqueous solution, without hydrogen peroxide, 90min dyestuff is handled when entering behavior, clearance after 30min
Up to 97%, fiber is taken out, after deionized water rinsing, is placed in air blast exsiccator, dried after 1h, put at 40 DEG C
Enter in the cationic blue aqueous solution that 10ml concentration is 20mg/L, without hydrogen peroxide, 90min dyestuff processing when entering behavior,
Clearance takes out fiber up to 96.8% after 30min, after deionized water rinsing, is placed in air blast exsiccator, at 40 DEG C
Dry after 1h, put it into the cationic blue aqueous solution that 10ml concentration is 20mg/L, without hydrogen peroxide, when entering behavior
Fiber is taken out up to 96.3%, after deionized water rinsing, is placed in drum by removal efficiency after 90min dyestuff processing, 30min
Air-dry in baking oven, dried at 40 DEG C after 1h, put it into the cationic blue aqueous solution that 10ml concentration is 20mg/L, without
Hydrogen peroxide, clearance, up to 96.7%, fiber is taken out, deionized water is used after 90min dyestuff processing, 30min when entering behavior
After flushing, it is placed in air blast exsiccator, is dried at 40 DEG C after 1h, puts it into the cationic blue water that 10ml concentration is 20mg/L
Solution, without hydrogen peroxide, 90min dyestuff processing when entering behavior, clearance takes out fiber up to 90.3% during 90min,
After deionized water rinsing, it is placed in air blast exsiccator, 1h is dried at 40 DEG C, produces fiber after the 9th reuse, 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 20mg/L cationic blue aqueous solution, 35ul hydrogen peroxide is added, clearance is up to 94.6% in 90min；And when hydrogen peroxide adds
When entering amount for 50ul, clearance is up to 97.1% in 90min；And when hydrogen peroxide addition is 100ul, clearance in 90min
Up to 97.3%；And when hydrogen peroxide addition is 200ul, clearance is up to 95.4% in 90min；And when hydrogen peroxide addition
During for 500ul, clearance 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, add clearance in 50ul hydrogen peroxide, 10min and, up to 96.8%, fiber is taken out, being directly placed into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, add clearance in 50ul hydrogen peroxide, 10min and, up to 97%, fiber is taken out, directly
Be put into the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 50ul hydrogen peroxide, in 10min clearance up to 97%,
Fiber is taken out, is directly placed into the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds in 50ul hydrogen peroxide, 10min
Clearance takes out fiber up to 95.8%, is directly placed into the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds
Clearance takes out fiber up to 92.5% in 50ul hydrogen peroxide, 10min, be directly placed into 10ml concentration for 20mg/L sun from
In the sub- indigo plant aqueous solution, add clearance in 50ul hydrogen peroxide, 10min and, up to 92.9%, fiber is taken out, 10ml is directly placed into dense
Spend in the cationic blue aqueous solution for 20mg/L, add clearance in 50ul hydrogen peroxide, 10min and, up to 84.7%, fiber is taken
Go out, being directly placed into 10ml concentration, clearance can in the 20mg/L cationic blue aqueous solution, to add in 50ul hydrogen peroxide, 10min
Up to 75.1%, fiber is taken out, is directly placed into the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 50ul dioxygens
Clearance is up to 70.2% in water, 10min；Fiber is taken out, the cationic blue that 10ml concentration is 20mg/L is directly placed into water-soluble
In liquid, add clearance in 50ul hydrogen peroxide, 10min and, up to 62%, fiber is taken out, after deionized water rinsing, drum is placed in
Air-dry in baking oven, 1h is dried at 40 DEG C, produce fiber after the 10th reuse, and can also continue to reuse.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% after 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, adds 500ul hydrogen peroxide, 90min when entering behavior
Dyestuff processing, clearance, until 90min clearances are up to 97.1%, fiber is taken out, spent up to 96.9% during 10min
Ionized water rinse after, be placed in air blast exsiccator, at 40 DEG C dry 1h after, put it into 10ml concentration for 20mg/L sun from
In the sub- indigo plant aqueous solution, add 500ul hydrogen peroxide, 90min dyestuff processing when entering behavior, during 12min clearance up to 95.7%,
Until 90min clearances are up to 96.9%, fiber is taken out, after deionized water rinsing, is placed in air blast exsiccator, at 40 DEG C
After lower dry 1h, put it into the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 500ul hydrogen peroxide, enter behavior
When 90min dyestuff processing, clearance, until 90min clearances are up to 85.7%, fiber is taken up to 82.3% during 20min
Go out, after deionized water rinsing, be placed in air blast exsiccator, dried at 40 DEG C after 1h, put it into 10ml concentration for 20mg/
In the L cationic blue aqueous solution, 500ul hydrogen peroxide is added, 90min dyestuff processing when entering behavior, until 90min clearances can
Up to 66.7%, fiber is taken out, after deionized water rinsing, is placed in air blast exsiccator, dries after 1h, is put at 40 DEG C
Enter in the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 500ul hydrogen peroxide, 90min dyestuff processing when entering behavior,
Until 90min clearances are up to 41.6%, fiber is taken out, after deionized water rinsing, is placed in air blast exsiccator, at 40 DEG C
Lower dry 1h, produces fiber after the 5th is reused, 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, b, weighs 30g n-BMAs, and be poured into above-mentioned beaker
In a, 0.2g benzoyl peroxides are weighed, is added it in above-mentioned beaker a, is weighed 0.05g benzoyl peroxides, be added into
Into above-mentioned beaker b, magnetic agitation is opened, until the benzoyl peroxide in beaker a, b is completely dissolved, hereafter, 50g bis- is weighed
NMF, is added in above-mentioned beaker a, opens magnetic agitation, makes the material mixing in beaker a uniform, then by beaker a
Middle solution is poured into polymeric kettle, the air for being passed through nitrogen to be remained in emptying polymeric kettle, is opened polymeric kettle heating system, is warming up to
85 DEG C, now the hydroxyethyl methacrylate containing initiator in beaker b is added drop-wise in polymeric kettle dropwise, time for adding is
0.5h, after completion of dropwise addition, continues to react 2h, after reaction terminates, resulting polymers solution A is moved in suitable beaker, sealed
It is standby；Above-mentioned n-BMA is replaced with n-butyl acrylate, above-mentioned experiment is repeated, after reaction terminates, is polymerize
Thing solution B, is placed in suitable beaker, seals standby；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 well mixed, well mixed solution is poured into wet spinning and contains liquid device
In, it will then contain liquid device and be placed in vacuum drier the deaeration under the conditions of 40 DEG C and -0.1MPa, the time is 30min, by compacted
Dynamic pump, which quantifies mixed solution, to be transported in spinning pack, and quantitative transporting velocity is 0.6ml/min, is formed after being extruded through spinneret orifice
Hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface is contacted with the coagulator in coagulating bath, in addition, by peristaltic pump by coagulator
It is transported to inside hollow dynamic analysis of spinning, it is contacted with hollow dynamic analysis of spinning inner surface, the speed of conveying coagulator is 0.9ml/
Min, coagulator is made up of deionized water, and under double diffusion effect, hollow dynamic analysis of spinning is cured as doughnut, by doughnut
The above is washed once in deionized water, is placed in air dry oven, 1h is dried under the conditions of 50 DEG C, and hollow fibre of coming into being is made
Dimension；Weigh 3.95g potassium permanganate, be placed on specification be 250ml volumetric flask in, then in above-mentioned volumetric flask add go from
Sub- water, configuration concentration is 0.1mol/L potassium permanganate solution, measures the above-mentioned potassium permanganate solutions of 9ml, is placed on suitable
In suitable beaker, 1g sodium hydroxides are weighed, and are added it in above-mentioned beaker, magnetic agitation is opened, makes sodium hydroxide completely molten
Solution, is made the mixed solution being made up of potassium permanganate, deionized water, sodium hydroxide, is placed in treatment trough, weighs 0.064g
Nascent doughnut, is immersed in mixed solution, and treatment trough temperature is increased into 80 DEG C, starts timing, to doughnut of coming into being
Post-processed, processing time is 30min, after post processing terminates, doughnut is taken out, deionized water cyclic washing is used, directly
To being fallen there is no black particle thing, then doughnut is placed in air dry oven, 1h is dried under the conditions of 30 DEG C, is made
Hollow fiber embryonic stem-like cells catalyst.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, without hydrogen peroxide, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 9% during 90min；Above-mentioned hollow fiber embryonic stem-like cells catalyst 0.1g is taken, is put into
10ml concentration is in the 20mg/L cationic blue aqueous solution, without hydrogen peroxide, 90min dyestuff is handled when entering behavior, 90min
When dyestuff clearance be only 68.0%, and the gained sample of embodiment 19 dyestuff clearance when reusing 9 times in this case
Still up to 90.3%.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation,
The clearance of cationic blue dyestuff is 39% during 90min；The above-mentioned hollow fiber embryonic stem-like cells catalyst of 0.024g is put
In the cationic blue aqueous solution that 10ml concentration is 20mg/L, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, during 90min
Cationic blue clearance takes out fiber up to 94.5%, after deionized water rinsing, is placed in air dry oven, at 40 DEG C
Under the conditions of dry 1h after, put it into 10ml concentration be 20mg/L the cationic blue aqueous solution in, add 500ul hydrogen peroxide,
Under the conditions of magnetic agitation, the clearance of cationic blue takes out fiber up to 79.3% during 90min, after deionized water rinsing,
It is placed in air dry oven, after drying 1h under the conditions of 40 DEG C, puts it into the cationic blue that 10ml concentration is 20mg/L water-soluble
In liquid, 500ul hydrogen peroxide is added, under the conditions of magnetic agitation, the clearance of cationic blue is up to 57.2% during 90min, by fiber
Take out, after deionized water rinsing, be placed in air dry oven, after drying 1h under the conditions of 40 DEG C, put it into 10ml concentration
In the 20mg/L cationic blue aqueous solution, to add 500ul hydrogen peroxide, under the conditions of magnetic agitation, cationic blue during 90min
Hollow fiber embryonic stem-like cells catalyst obtained by clearance close to 39%, i.e. comparative example is only capable of repeating to make under these conditions
With 3 times, and the gained sample of embodiment 19 then can be reused at least 5 times in this case.
Claims (8)
1. a kind of manufacture 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：The quality monomers 1 such as two parts are weighed, is placed on respectively in suitable beaker a, b, weighs monomer
2, it is 0.01: 9.99~9.99: 0.01 to make the ratio between gross mass of monomer 2 and two parts of monomers 1, and monomer 2 is poured into above-mentioned beaker a
In, initiator is weighed, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and initiator is added
Enter into beaker a, initiator is weighed again, current initiator quality is 0.2~2% of the mass of monomer 1 in beaker b, and is added
To beaker b, open magnetic agitation, until initiator is completely dissolved in beaker a, b, weigh solvent, make solvent and two parts of monomers 1 with
And the ratio between the gross mass of monomer 2 is 1: 5~5: 1, and solvent is added in above-mentioned beaker a, opens magnetic agitation, make in beaker a
Material mixing is uniform, then goes in polymeric kettle solution in beaker a, is passed through nitrogen with residual air in emptying polymeric kettle, opens
Polymeric kettle heating system is opened, 50~100 DEG C are warming up to, the monomer 1 containing initiator in beaker b is now added drop-wise to polymeric kettle dropwise
In, time for adding is controlled within 10~60min, after completion of dropwise addition, is continued to react 2~6h, polymer solution A is obtained, by gained
Polymer solution A is transferred in suitable beaker, is sealed standby, is changed above-mentioned monomer 2 into monomer 3, performs above-mentioned polymerization procedure,
Polymer solution B is obtained, resulting polymers solution B is transferred in suitable beaker, and seal standby；
(2) wet spinning technology：By above-mentioned steps (1) resulting polymers solution A, B using volume ratio as 99.99: 0.01~0.01:
99.99 are mixed, and by mixture 0.5~3h of magnetic agitation, to be well mixed, gained mixed solution is poured into Wet-spinning
Silk contain liquid device in, then will contain liquid device be placed in vacuum drier under the conditions of 25~95 DEG C and -0.07~-0.1MPa take off
Bubble, the time is 0~60min, quantifies mixed solution by peristaltic pump and is transported in spinning pack, is formed after being extruded through spinneret orifice
Hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface is contacted with the coagulator in coagulating bath, in addition, by peristaltic pump by coagulator
Quantitatively it is transported to inside hollow dynamic analysis of spinning, it is contacted with hollow dynamic analysis of spinning inner surface, coagulator is by deionized water and molten
Agent is constituted, and the mass ratio of deionized water and solvent is 10: 0~5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is cured as
Doughnut, the above is washed once by doughnut in deionized water, is placed in air dry oven, in 25~50 DEG C of conditions
1~6h of lower drying, is made nascent doughnut；
(3) acidic hydrolysis technique：Doughnut made from taking above-mentioned steps (2), is placed on 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 fully washing, and dry；
(4) neutral potassium permanganate oxidation reduction treatment technique：The potassium permanganate of certain mass is weighed, is placed in volumetric flask,
Certain volume deionized water is added, configuration concentration is 0.0001~0.3mol/L potassium permanganate solution, measures certain volume
Above-mentioned potassium permanganate solution, and be placed in treatment trough, doughnut is placed in processing after being hydrolyzed obtained by above-mentioned steps (3)
In groove, 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 processing time is 30s~8h, after processing terminates, and takes out doughnut,
Deionized water cyclic washing is used, until cleaning solution is there is no color, then doughnut is placed in vacuum drier in 25~
1~6h is dried under the conditions of 50 DEG C, hollow fiber out-phase embryonic stem-like cells catalyst is made.
2. a kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, it is special
Levy and be that described monomer 1 is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, acrylic acid hydroxypropyl
One kind in ester.
3. a kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, it is special
Levy and be described monomer 2 for methyl methacrylate, EMA, 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 kind in six esters, octadecyl methacrylate.
4. a kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, it is special
Levy and be that described 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 kind in sour isodecyl ester, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate.
5. a kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, it is special
Levy be described initiator for benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, TBHP,
One kind in cumyl peroxide, di-t-butyl peroxide.
6. a kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, it is special
Levy and be described solvent in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene
One kind.
7. a kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst according to claim 1, it is special
Levy and be that described inorganic acid is one kind in the concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid, concentrated phosphoric acid.
8. according to a kind of system of hollow fiber out-phase embryonic stem-like cells catalyst according to any one of claims 1 to 7
Make method, it is characterised in that described monomer 1 is hydroxyethyl methacrylate, described monomer 2 is n-BMA,
Described monomer 3 is n-butyl acrylate, and described initiator is benzoyl peroxide, and described solvent is dimethyl formyl
Amine, described inorganic acid is the concentrated sulfuric acid.
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| CN113354838A (en) * | 2021-06-04 | 2021-09-07 | 深圳大学 | Hydrogel with Fenton catalytic property and preparation method and application thereof |
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