CN105970353A - Preparation method for decomposing hollow fibers of dyes through catalytic oxidation - Google Patents
Preparation method for decomposing hollow fibers of dyes through catalytic oxidation Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a preparation method capable of rapidly and efficiently decomposing hollow fibers of various dyes through oxidation by catalyzing an oxidizing agent, belonging to the technical field of fiber preparation. The preparation method is characterized by firstly synthesizing a polyacrylate (polymethacrylate) solution by adopting solution polymerization, then preparing polyacrylate (polymethacrylate) hollow fibers with inner and outer surfaces rich in hydroxy by adopting a wet spinning process and then under alkaline conditions, preparing a composite hollow fiber with polyacrylate (polymethacrylate) as a skeleton and manganite as a supporter based on corrosion of alkali liquor from the outside to the inside, redox reaction between hydroxy and potassium permanganate and strong complexation between generated carboxyl and manganite. The composite hollow fiber not only has the characteristic of catalyzing the oxidizing agent to decompose the dyes through oxidation but also can be directly separated from water bodies during application and has very large specific surface area, so the composite hollow fiber has the advantages of high catalytic activity, high processing speed, high dye removal rate, and the like and has a broader application prospect in the field of dye wastewater treatment.
Description
Technical field
The present invention relates to the manufacturing technology of a kind of doughnut, specially one can catalytic oxidant rapidly and efficiently oxygen
Change decompose multiple dyestuff doughnut manufacture method, this manufacture method make use of polymerisation in solution, wet spinning with
And the technology such as potassium permanganate process under the conditions of alkalescence.
Background technology
Water is the indispensable natural resourcess of the mankind, and water resource is the basis of social development, is also economic development
Necessary resources.The war that water pollution control and fwaater resources protection have become as China at present or even the whole world is paid close attention to jointly
Slightly one of problem.China's gross amount of water resources 2.8 tcm, occupies the 4th, the world, accounts for world water resources total
The 7% of amount.But China's water resource of per capita only 2300 cubic metres, only the 1/4 of world average level, China
Water resource of per capita occupies the 82nd in 132 countries that the World Bank adds up in recent years, belongs to water scarcity
Country, moreover, our distribution of water resources is the most uneven, north water resource of per capita only 995 cubic metres,
Belong to areas of serious, although and southwest and south each province water resource of per capita are more than 3000 cubic metres, but
Water resource still suffers from the problems such as skewness, and some areas water is seriously polluted, creates water quality hydropenia (field
Li Li, Jiang Bo, Fu Yi, whole nation Water Pollution Problem analysis, Heilungkiang scientific and technological information, 2012 (25): 61-61).
The geometric growth of the size of population, modern industry waste water unrest row leave about, municipal refuse, rural area pesticide spraying etc.,
Causing has been few freshwater resources aggravation shortage originally, it is impossible to used by people, China's contaminant water 70%～80%
Directly discharge, annual blowdown flow rate about 30,000,000,000 tons, and the disposal ability of sewage only account for about 20% (Xu Jianing,
Chen Yan, China's Water Pollution Problem, Guangdong chemical industry, 2014,41 (3): 143-144).Textile and dyeing industry,
As one of China's advantageous conventional column industry, since the nineties in 20th century, obtain fast development,
Its water requirement and displacement also increase substantially, and according to statistics, China produces dyeing waste water every year and is about 1,600,000,000 tons,
Occupy the whole discharged volume of industrial waste water of China the 6th, along with the development of processing technique and new dye, auxiliary agent not
Disconnecting and send out application, the intractability of dyeing waste water is also increasing, dashing forward by water and drainage problem mesh benefit of dyeing
Go out (Dong Jianwei, dyeing waste water advanced treating and reuse technology research, Guangdong chemical industry, 2014,41 (1): 106-107).
Dyeing waste water has the features such as the water yield is big, organic pollution content is high, colourity is deep, alkalescence is big, change of water quality is big,
Belong 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 becomes, and Zhang Liang etc. is smelly
Oxygen catalytic oxidation technique advanced treatment of dyeing wastewater, environmental project journal, 2013,7 (8): 2873-2876).
Dyestuff in dyeing waste water can absorb light, reduces water transparency, affects aquatile and growth of microorganism,
Being unfavorable for the self-purification of water, easily cause visual pollution simultaneously, the water body of severe contamination influences whether that the mankind's is strong
Health, has come great potential safety hazard (Papa M, Alfons for mankind's living zoneN C, Moreira M T,
Et al, Ranking wastewater treatment trains based on their impacts and benefits on
Human health:a " Biological Assay and Disease " approach, Journal of Cleaner
Production, 2016,113:311-317；Sze-Mun Lam, Jin-Chung Sin, Abdul Rahman
Mohamed, A review on photocatalytic application of g-C3N4/semiconductor (CNS)
Nanocomposites towards the erasure of dyeing wastewater, Materials Science in
Semiconductor Processing, 2016,47:62-84；Zhu Hongfei, Li Dinglong, Zhu Chuanwei, printing and dyeing are useless
The harm of water and watershed management behave, environmental science and management, 2007,32 (11): 89-92), therefore,
Removing the various dyestuffs in waste water the most quickly and efficiently is the primary difficult problem faced at present.
At present, the method such as industrial commonly used physical chemistry (such as absorption, flocculation) and biology processes dyestuff etc.
Organic pollution, wherein physico-chemical process has the advantages such as equipment is simple, easy and simple to handle, but this type of method is led to
It is often only that the Organic substances such as dyestuff are transferred to solid phase (such as activated carbon adsorption) from liquid phase, has not been completely eliminated
Organic pollutants, and substantial amounts of solid waste and regenerative wastewater can be brought, therefore, at removal effect and secondary
All there is certain defect (Ali I, Asim M, Khan TA, Low cost adsorbents in the aspects such as pollution
The removal of organic pollutants from wastewater, Journal of Environmental
Management, 2012,113 (1): 170-183).Bioanalysis has the advantages such as operating cost is low, but deposits
Big at long processing period, hold facility area, biological toxic action can be caused by the organic pollution such as dyestuff
Except problems such as poor effect, be also possible to generate under conditions of anaerobism carcinogenic aromatic amine compounds (Fan J,
Li H, Shuang C, et al, Dissolved organic matter removal using magnetic anion
Exchange resin treatment on biological effluent of textile dyeing wastewater, Journal
Of Environmental Sciences, 2014,26 (8): 1567-1574；Lv Wangyang, catalysis fiber degradation
The research of the organic pollutions such as dyestuff, Institutes Of Technology Of Zhejiang, 2010).Compared to the above, catalysis oxidation
Decomposition technique will be each by the strong oxidizing property living radical (such as hydroxyl radical free radical, superoxide radical etc.) produced
Plant dye oxidation, and then make dye molecule resolve into the mankind and environmentally friendly small-molecule substance (Ru Shui and two
Carbonoxide etc.), and it is short to have the response time, treatment effeciency is high, and product does not results in the advantages such as secondary pollution,
Therefore, catalysis oxidation Decomposition technology causes the concern of people day by day.
Titanium dioxide (TiO2), as the photocatalyst of function admirable, there is nontoxic, catalysis activity height, oxygen
The features such as change ability is strong, good stability, corrosion-resistant, easily prepared and use, therefore, with TiO2Based on
The catalysis oxidation Decomposition technology of material receives publicity, and it is in the difficult fall such as dyestuff, papermaking, coking, process hides, pharmacy
Solve waste water treatment field to be applied.While it is true, TiO2The application of photocatalyst still suffers from two big key skills
An art difficult problem: 1. TiO2Greater band gap, only with ultraviolet portion a small amount of in sunlight, photoresponse model
Enclose narrower；2. after photocatalyst light excites, the electron-hole pair poor stability of generation, it is susceptible to phase body
Inside and outside is compound, and photon utilization rate reduces (Zhao Huan, mesoporous TiO2The preparation of composite photo-catalyst and photocatalysis
The research of degradation of dye waste water, Chang An University, 2013).Zinc oxide (ZnO) has and TiO2Similar
Energy gap, has again with low cost simultaneously, and preparation technology is simple, and nontoxic, pollution-free, degradation efficiency is higher
Etc. advantage, become the appropriately selected of extensive treatment of Organic Wastewater, but ZnO only absorbs ultraviolet light, Er Qie
Under ultraviolet light irradiates, ZnO can occur photoetch, solubilized, its photocatalysis performance again under extreme pH value
Largely affected by factors such as this body structure of material, particle size, pattern, defect kind and concentration,
And these factors are affected (Li Meng, the preparation of different-shape ZnO material by material preparation method further
And Photocatalytic Performance Study, He'nan Normal University, 2013；Zhou Mojiao, zinc oxide base nano composite can
Control synthesis and Photocatalytic Performance Study thereof, Zhejiang Normal University, 2013), therefore, the application of ZnO is also subject to
Limit.Use Fenton reagent can effectively process various waste water from dyestuff (Shi Penghui, heterogeneous
The research of Co3O4/GO/PMS system catalyzing oxidizing degrading waste water from dyestuff, Donghua University, 2013), but also
There is various shortcoming and restriction: 1. Fenton reagent method and the most most widely used biological treatment
Method, flocculence etc. compare, and processing cost is higher, this is because, Fenton reagent is relatively costly, and Fenton
The restriction (such as pH value, temperature, the impact etc. of inorganic ions) of reaction condition too increases the process of waste water
Cost；2. the H that the permineralization of unit waste water adds needed for processing2O2Amount is all far above calculated value, explanation
Production rate and the utilization rate of hydroxyl radical free radical (OH) are the highest；3. Fenton reagent method processes the height of waste water from dyestuff
Effect property is at strict response system acid-base value (pH value), H2O2With Fe2+The reaction bar such as dosage and ratio
Realize under part, because of containing Fe in the water outlet after process3+Ion and with color, there is serious secondary pollution
(research of Li Hong, Fenton high-level oxidation technology oxidative degradation multiring aromatic hydrocarbon waste water from dyestuff, Chongqing is big for problem
Learn, 2007), these shortcomings limit the large-scale application of Fenton reagent method.Mn oxide, has excellent
Different catalysis activity, and there is the advantages such as raw material sources are wide, processing technique is simple, production cost is low, it is in dye
Material waste water treatment field can play the most positive effect, is possible not only to process multiple dye wastewater with high concentration, and
And processing method possesses without implementing under illumination, non-secondary pollution, room temperature, cheap, mineral origin
Extensively, the plurality of advantages such as percent of decolourization is high, COD clearance is high, therefore, utilize Mn oxide to process dyestuff and give up
Water paid close attention to widely (Wang Zheng, Mn oxide to the absorption of methylene blue dyestuff and oxidative decoloration research, in
Ocean university of state, 2007；Li Hongyan, the mesoporous and preparation of hollow-core construction Mn oxide and catalytic performance thereof grind
Study carefully, HeFei University of Technology, 2010).Although Mn oxide has the most prominent at catalysis oxidation Decomposition dye field
The price advantage gone out, but the Mn oxide prepared at present mostly is powder or graininess, is catalyzed oxidation Decomposition dyestuff
After, easily residue in water body, need to separate by the means such as filtering, centrifugal, improve application cost, limit
Its application, therefore, the Mn oxide base catalysis material that research and development can directly separate with water body has important
Practical significance.
The Mn oxide base catalysis material that can directly separate with water body for acquisition, gives catalysis material bigger simultaneously
Specific surface area, the present invention as monomer, uses solution polymerization process to synthesize poly-(first with (methyl) esters of acrylic acid material
Base) acrylate solution, subsequently with this solution as spinning solution, by the filament spinning component of designed, designed, use
Wet spinning technology prepares surfaces externally and internally all rich in poly-(methyl) acrylate doughnut of hydroxyl, then exists
Under the conditions of alkalescence, anti-based on the oxidoreduction between alkali liquor etching and hydroxyl and potassium permanganate from outward appearance to inner essence
Should, potassium permanganate is reduced and generates Mn oxide, and hydroxyl is oxidized and generates carboxylic acid group, Mn oxide and carboxylic
There is strong complexing between acidic group, result makes the Mn oxide of generation not only be securely joined with appearance in fiber
Face, but also be carried in the hole between surfaces externally and internally, prepare with poly-(methyl) acrylate as skeleton,
Mn oxide is the composite hollow fibre of loaded article, and composite hollow fibre not only has catalytic oxidant oxidation Decomposition
The characteristic of dyestuff, and can directly separate with water body when applying, its specific surface area is also very big, therefore, has again
Catalysis activity is high, and processing speed is fast, dyestuff clearance advantages of higher, administers field at waste water from dyestuff and has more
Wide application prospect.
Summary of the invention
For the deficiencies in the prior art, the technical problem that the present invention intends to solve is to provide one can catalytic oxidant
The rapidly and efficiently manufacture method of oxidation Decomposition multiple dyestuff doughnut.It is suitable that first this manufacture method selects
(methyl) acrylate monomer, by control polymerization technique, use solution polymerization process synthesis rich in hydroxyl can
Wet spinning poly-(methyl) acrylate solution, subsequently with this solution as spinning solution, by designed, designed
Filament spinning component, uses wet spinning technology to prepare surfaces externally and internally all rich in poly-(methyl) acrylate of hydroxyl
Hollow fiber, the most in the basic conditions, between alkali liquor etching and hydroxyl and potassium permanganate from outward appearance to inner essence
Redox reaction, potassium permanganate is reduced and generates Mn oxide, and hydroxyl is oxidized and generates carboxylic acid group,
There is strong complexing between Mn oxide and carboxylic acid group, result makes the Mn oxide of generation not only be securely joined with
In fiber surfaces externally and internally, but also it is carried in the hole between surfaces externally and internally, prepares with poly-(methyl) propylene
Acid esters is skeleton, and Mn oxide is the composite hollow fibre of loaded article.Gained composite hollow fibre and existing powder
Shape or graininess Mn oxide material are compared, and have low cost, recovery easy to use, easy, do not easily cause secondary
Pollute, processing and manufacturing can become the advantages such as variform product；With compared with type wet spinning process solid fibers,
Gained composite hollow fibre has bigger specific surface area, can load more Mn oxide, catalytic oxidant oxygen
The efficiency changing disperse dyes significantly improves, and application cost significantly reduces, and therefore, more meets industrial applicibility and wants
Ask.
The present invention solves the technical scheme of described technical problem: design one can catalytic oxidant rapidly and efficiently oxygen
Changing the manufacture method decomposing multiple dyestuff doughnut, its technical process is as follows:
(1) solution polymerization process: weigh the quality monomers 1 such as two parts, be placed on suitable beaker a respectively, b
In, weighing monomer 2, the ratio making the 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 in above-mentioned a beaker, weigh initiator, making initiator quality is monomer 1 He in beaker a
The 0.2～2% of monomer 2 gross mass, and initiator is added beaker a, again weigh initiator, cause specifically
Agent quality is in beaker b the 0.2～2% of monomer 1 mass, and adds beaker b, opens magnetic agitation, until
Beaker a, in b, initiator is completely dissolved, and weighs solvent, makes solvent and two parts of monomers 1 and the total matter of monomer 2
The ratio of amount is 1: 5～5: 1, and is joined by solvent in above-mentioned beaker a, opens magnetic agitation, makes in beaker a
Material mix homogeneously, pours in polymeric kettle by solution in beaker a subsequently, is passed through nitrogen with residual in emptying polymeric kettle
Leave a blank gas, open polymeric kettle heating system, be warming up to 50～100 DEG C, now will be containing initiator in beaker b
Monomer 1 is progressively added drop-wise in polymeric kettle, and time for adding controls, within 10～60min, after completion of dropwise addition, to continue
Continuous reaction 2～6h, obtains polymer solution A, resulting polymers solution A is moved in suitable beaker, seals
Standby, change above-mentioned monomer 2 into monomer 3, obtain polymer solution B, and seal standby；
Described monomer 1 is hydroxyethyl methylacrylate, 2-(Acryloyloxy)ethanol, Hydroxypropyl methacrylate, propylene
One in acid hydroxypropyl fat；
Described monomer 2 is methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl-prop
The most own ester of olefin(e) acid N-butyl, isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid, methyl
N-octyl, 2-Propenoic acid, 2-methyl-, isooctyl ester, isodecyl methacrylate, lauryl methacrylate, first
One in base tetradecyl acrylate, hexadecyl metrhacrylate, octadecyl methacrylate；
Described monomer 3 is acrylic acid methyl ester., ethyl acrylate, propyl acrylate, n-butyl acrylate, propylene
Acid isobutyl ester, tert-butyl acrylate, the most own ester of acrylic acid, acrylic acid 1 Octyl Nitrite, acrylic acid are the most pungent
Ester, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, acrylic acid 16
One in ester, octadecyl acrylate；
Described initiator is benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, t-butyl peroxy
Change the one in hydrogen, cumyl peroxide, di-t-butyl peroxide；
Described solvent be dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide, toluene, dimethylbenzene, four
One in vinyl chloride；
(2) wet spinning technology: with volume ratio be by above-mentioned steps (1) resulting polymers solution A, B
99.99: 0.01～0.01: 99.99 mixes, and by mixture magnetic agitation 1～3h, in order to mix homogeneously,
Gained mixed solution is poured into wet spinning contain in liquid device, subsequently Sheng liquid device is placed in vacuum drier
Deaeration under the conditions of 25～95 DEG C and-0.07～-0.1MPa, the time is 0～60min, will be mixed by peristaltic pump
Closing solution to be quantitatively transported in spinning pack, quantitative transporting velocity is 0.2～2ml/min, after spinneret orifice is extruded
Forming hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface contacts with the coagulator in coagulating bath, additionally, pass through
Coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump so that it is contact with hollow dynamic analysis of spinning inner surface, defeated
The speed sending coagulator is 0.5～5ml/min, and coagulator is made up of deionized water and solvent, deionized water and molten
The mass ratio of agent is 10: 0～5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is cured as doughnut,
Doughnut be washed once in deionized water above, be placed in air dry oven, at 25～50 DEG C of bars
It is dried 1～6h under part, prepares nascent doughnut；
Described solvent be dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide, toluene, dimethylbenzene, four
One in vinyl chloride；
(3) aftertreatment technology: weigh the potassium permanganate of certain mass, is placed in volumetric flask, adds one
Determining volumes of deionized water, configuration concentration is the potassium permanganate solution of 0.01～10mol/L, measures certain volume
Above-mentioned potassium permanganate solution, is placed in suitable beaker, weighs the water soluble alkali of certain mass, makes solvable
The property quality of alkali is 1: 5～1: 20 with the ratio of the volume of potassium permanganate solution, and is joined by water soluble alkali
State in beaker, open magnetic agitation, make water soluble alkali be completely dissolved, prepare by potassium permanganate, deionized water,
The mixed solution of water soluble alkali composition, weighs the above-mentioned mixed solution of certain mass, is placed in treatment trough,
Weigh the nascent doughnut of certain mass, make the nascent doughnut with above-mentioned mixed solution mass ratio be
1: 5～1: 50, and nascent doughnut is placed in treatment trough so that it is it is immersed in mixed solution, by treatment trough
Temperature is increased to 25～95 DEG C, starts timing, nascent doughnut is carried out post processing, and finishing time is
5min～6h, after post processing terminates, takes out nascent doughnut, uses deionized water cyclic washing, until not
There is black particle thing to fall again, subsequently nascent doughnut is placed in air dry oven, at 25～50 DEG C of bars
Being dried 1～6h under part, preparing can the doughnut of the catalytic oxidant multiple dyestuff of rapidly and efficiently oxidation Decomposition；
Described water soluble alkali is the one in sodium hydroxide, Lithium hydrate, potassium hydroxide, barium hydroxide.
Compared with prior art products, first, gained doughnut of the present invention morphologically has outstanding advantage,
The Mn oxide prepared at present mostly is powder or graininess, after catalytic oxidant oxidation Decomposition dyestuff, and these manganese
Oxide easily residues in water body, need to separate by the means such as filtering, centrifugal, and application cost is obviously improved, and
Gained doughnut of the present invention can directly take out after using from water, and drying processes, and can repeatedly utilize, and reduces
Use cost, and variform product can be processed into, can meet the different application field demand to form；With
Compared with type wet spinning process solid fibers, gained doughnut of the present invention has bigger specific surface area, can
Loading more Mn oxide, the efficiency of catalytic oxidant oxidation Decomposition dyestuff significantly improves, and application cost is notable
Reducing, additionally, gained doughnut of the present invention can directly carry the circulation of waste water from dyestuff, waste water from dyestuff is in hollow
During fibrous inside flowing, a step can complete the catalysis oxidation Decomposition of dyestuff, after exit directly collection processes
Water purification；Secondly, in preparation method novel aspects, the present invention also has an outstanding advantage, existing powder or
Particulate manganese oxides material is generally prepared by hydro-thermal method, sol-gal process, solid phase method etc., the productivity generally having
Low, the problem such as severe reaction conditions limits powder or the large-scale production of graininess Mn oxide material, and
Present invention step in treatment trough achieves the reaction such as Mn oxide, carboxylic acid group's generation, be simultaneously based on carboxylic acid cloudy from
Strong complexing between son and Mn oxide achieves the strong bonded of Mn oxide thin layer and matrix polymer, tool
Respond mild condition, low for equipment requirements, productivity advantages of higher；Finally, in the range of applicant retrieves,
There is not yet employing technique manufacture of the present invention can be in the catalytic oxidant multiple dyestuff of rapidly and efficiently oxidation Decomposition
The pertinent literature report of hollow fiber.
Detailed description of the invention
It is further discussed below the present invention: what the present invention designed can catalytic oxidant rapidly and efficiently oxygen below in conjunction with embodiment
The manufacture method (hereinafter referred to as manufacture method) changing the multiple dyestuff doughnut of decomposition relates to polymerisation in solution, wet method
The integrated application of the technology such as potassium permanganate process under the conditions of spinning and alkalescence, it is intended to solve existing powder or
Particulate manganese oxides when processing that form present in waste water from dyestuff is single, reclaiming because of need to by filtering, centrifugal etc.
Technological means and cost is high, be difficult to problems such as being used for multiple times, solve the same solid fibre of type wet spinning process simultaneously
The problems such as the specific surface area that dimension exists is little, complexation Mn oxide is few, catalytic efficiency is low, carry for dye wastewater treatment
For a kind of new material, its technical process or step are as follows:
(1) solution polymerization process: weigh the quality monomers 1 such as two parts, be placed on suitable beaker a respectively,
In b, weighing monomer 2, the ratio making the 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 in above-mentioned a beaker, weigh initiator, making initiator quality is monomer 1 He in beaker a
The 0.2～2% of monomer 2 gross mass, and initiator is added beaker a, again weigh initiator, cause specifically
Agent quality is in beaker b the 0.2～2% of monomer 1 mass, and adds beaker b, opens magnetic agitation, until
Beaker a, in b, initiator is completely dissolved, and weighs solvent, makes solvent and two parts of monomers 1 and the total matter of monomer 2
The ratio of amount is 1: 5～5: 1, and is joined by solvent in above-mentioned beaker a, opens magnetic agitation, makes in beaker a
Material mix homogeneously, pours in polymeric kettle by solution in beaker a subsequently, is passed through nitrogen with residual in emptying polymeric kettle
Leave a blank gas, open polymeric kettle heating system, be warming up to 50～100 DEG C, now will be containing initiator in beaker b
Monomer 1 is progressively added drop-wise in polymeric kettle, and time for adding controls, within 10～60min, after completion of dropwise addition, to continue
Continuous reaction 2～6h, obtains polymer solution A, resulting polymers solution A is moved in suitable beaker, seals
Standby, change above-mentioned monomer 2 into monomer 3, obtain polymer solution B, and seal standby；
(2) wet spinning technology: with volume ratio be by above-mentioned steps (1) resulting polymers solution A, B
99.99: 0.01～0.01: 99.99 mixes, and by mixture magnetic agitation 1～3h, in order to mix homogeneously,
Gained mixed solution is poured into wet spinning contain in liquid device, subsequently Sheng liquid device is placed in vacuum drier
Deaeration under the conditions of 25～95 DEG C and-0.07～-0.1MPa, the time is 0～60min, will be mixed by peristaltic pump
Closing solution to be quantitatively transported in spinning pack, quantitative transporting velocity is 0.2～2ml/min, after spinneret orifice is extruded
Forming hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface contacts with the coagulator in coagulating bath, additionally, pass through
Coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump so that it is contact with hollow dynamic analysis of spinning inner surface, defeated
The speed sending coagulator is 0.5～5ml/min, and coagulator is made up of deionized water and solvent, deionized water and molten
The mass ratio of agent is 10: 0～5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is cured as doughnut,
Doughnut be washed once in deionized water above, be placed in air dry oven, at 25～50 DEG C of bars
It is dried 1～6h under part, prepares nascent doughnut；
(3) aftertreatment technology: weigh the potassium permanganate of certain mass, is placed in volumetric flask, adds one
Determining volumes of deionized water, configuration concentration is the potassium permanganate solution of 0.01～10mol/L, measures certain volume
Above-mentioned potassium permanganate solution, is placed in suitable beaker, weighs the water soluble alkali of certain mass, makes solvable
The property quality of alkali is 1: 5～1: 20 with the ratio of the volume of potassium permanganate solution, and is joined by water soluble alkali
State in beaker, open magnetic agitation, make water soluble alkali be completely dissolved, prepare by potassium permanganate, deionized water,
The mixed solution of water soluble alkali composition, weighs the above-mentioned mixed solution of certain mass, is placed in treatment trough,
Weigh the nascent doughnut of certain mass, make the nascent doughnut with above-mentioned mixed solution mass ratio be
1: 5～1: 50, and nascent doughnut is placed in treatment trough so that it is it is immersed in mixed solution, by treatment trough
Temperature is increased to 25～95 DEG C, starts timing, nascent doughnut is carried out post processing, and finishing time is
5min～6h, after post processing terminates, takes out nascent doughnut, uses deionized water cyclic washing, until not
There is black particle thing to fall again, subsequently nascent doughnut is placed in air dry oven, at 25～50 DEG C of bars
Being dried 1～6h under part, preparing can the doughnut of the catalytic oxidant multiple dyestuff of rapidly and efficiently oxidation Decomposition.
Monomer 1 described in manufacture method of the present invention is hydroxyethyl methylacrylate, 2-(Acryloyloxy)ethanol, methyl-prop
One in olefin(e) acid hydroxypropyl acrylate, hydroxypropyl acrylate.The effect of monomer 1 is as follows: 1. introduce hydroxyl, and hydroxyl is made
For reducing agent, with potassium permanganate generation redox reaction, it is achieved the in-situ preparation of Mn oxide, hydroxyl is at height
Carboxyl, carboxyl and generated in-situ Mn oxide complexation it is oxidized to, it is achieved doughnut pair under potassium manganate effect
The load of Mn oxide；2. the hydrophilicity of doughnut is improved, it is simple to the process of waste water from dyestuff；3. improve molten
Monomer conversion during liquid polymerization, the polymer molecular weight that narrows is distributed, improves the spinning spinnability of polymer.
The preferred hydroxyethyl methylacrylate of monomer 1 described in manufacture method of the present invention, reason is as follows: with acrylic acid hydroxyl second
Ester, Hydroxypropyl methacrylate, Hydroxypropyl acrylate are compared, and hydroxyethyl methylacrylate is nontoxic chemical reagent,
Human body will not be produced harm.
Monomer 2 described in manufacture method of the present invention is methyl methacrylate, ethyl methacrylate, methyl-prop
Olefin(e) acid propyl ester, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, methyl-prop
The most own ester of olefin(e) acid, n octyl methacrylate, 2-Propenoic acid, 2-methyl-, isooctyl ester, isodecyl methacrylate, methyl
In dodecyl acrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, octadecyl methacrylate
A kind of.The effect of monomer 2 is as follows: 1. the homopolymer solution of monomer 2 has preferable spinning spinnability, therefore single
The introducing of body 2 can improve the spinning spinnability of polymer solution, beneficially wet spinning and shape；2. monomer is destroyed
Hydrogen bond action between 1 and solvent, improves rate of polymerization, the homopolymerization of suppression monomer 1, makes polymerization system generate altogether
Polymers.The preferred n-BMA of monomer 2 described in manufacture method of the present invention, reason is as follows: 1. with first
Base acrylic acid methyl ester., ethyl methacrylate, propyl methacrylate are compared, and n-BMA is more easy to
In being copolymerized with monomer 2, and abnormal smells from the patient is less, and reaction condition is gentleer, it is easy to controls polymerization process, does not deposits
In implode, the phenomenon such as highly exothermic；2. with isobutyl methacrylate, Tert-butyl Methacrylate, methyl-prop
The most own ester of olefin(e) acid, n octyl methacrylate, 2-Propenoic acid, 2-methyl-, isooctyl ester, isodecyl methacrylate, methyl
Dodecyl acrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, octadecyl methacrylate ester phase
Ratio, n-BMA side chain lengths is suitable, can give the glass transition temperature that polymer is moderate after polymerization
Degree so that it is there is the pliability of excellence, suitable elasticity, more prominent intensity.
Monomer 3 described in manufacture method of the present invention is acrylic acid methyl ester., ethyl acrylate, propyl acrylate, third
The most own ester of olefin(e) acid N-butyl, Isobutyl 2-propenoate, tert-butyl acrylate, acrylic acid, acrylic acid 1 ethyl
Own ester, n-octyl, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, acrylic acid ten
One in four esters, Process Conditions of Cetane Acrylate, octadecyl acrylate.The effect of monomer 3 is as follows: 1. monomer 3
Homopolymer there is fabulous pliability, prominent elasticity, thus the introducing of monomer 3 can be substantially improved hollow fine
The pliability of dimension and elasticity, beneficially the carrying out of post processing, make final doughnut have the most practical power
Learn performance；2. destroy the hydrogen bond action between monomer 1 and solvent, improve rate of polymerization, suppress the homopolymerization of monomer 1,
Make polymerization system generate copolymer, in last handling process, accelerate alkali liquor etching from outward appearance to inner essence, occur simultaneously
Hydrolyze and introduce more hydroxy-acid group, make doughnut load more Mn oxide.Manufacture method of the present invention
The described preferred n-butyl acrylate of monomer 3, reason is as follows: 1. with acrylic acid methyl ester., ethyl acrylate, third
Olefin(e) acid propyl ester is compared, and the polymer that n-butyl acrylate generates has preferable pliability and lower temperature resistance, more has
It is beneficial to improve the mechanical property of doughnut and resistance to low temperature；2. with Isobutyl 2-propenoate, the tertiary fourth of acrylic acid
Ester is compared, and the polymer strands that n-butyl acrylate generates is best, beneficially spinning technique；3. with acrylic acid
The most own ester, acrylic acid 1 Octyl Nitrite, n-octyl, Isooctyl acrylate monomer, isodecyl acrylate,
Dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate long alkyl chain ester are compared,
N-butyl acrylate is short alkyl chain ester, during long alkyl chain polyisocyanate polyaddition, owing to glass transition temperature is extremely low, raw
The polymer become is the most soft viscous, and the later stage is the most viscous in the reaction and becomes bulk, even becomes because of moment implode
Roll into a ball and cause the failure of polymerization, during the polymerization of short alkyl chain ester n-butyl acrylate, the most there are not the problems referred to above.
Initiator described in manufacture method of the present invention is benzoyl peroxide, azodiisobutyronitrile, isopropylbenzene peroxide
Change the one in hydrogen, tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide.Select to cause
The principle of agent includes: 1. according to the initiator that the polymerization temperature selection half-life is suitable, make polymerization time moderate, choosing
Use the initiator that highly active initiator, i.e. half-life are shorter, to improve rate of polymerization, shorten polymerization time,
Polymerization temperature can be reduced simultaneously and reduce initiator amount；2. it should also be taken into account that initiator to polymer quality with or without
Impact, initiator have in avirulence, use and storage process whether security problems, it is well known that peroxidating
The di-t-butyl half-life when 100 DEG C is 218h, and the cumyl peroxide half-life when 115 DEG C is
12.3h, the tert-butyl hydroperoxide half-life when 154.5 DEG C is 44.8h, and isopropyl benzene hydroperoxide is at 125 DEG C
Time half-life be 21h, the azodiisobutyronitrile half-life when 100 DEG C is 0.1h, and benzoyl peroxide exists
Half-life when 125 DEG C is 0.42h, and temperature reduces Increased Plasma Half-life, and temperature raises half life.This
The range of reaction temperature that bright solution polymerization process relates to is 50～100 DEG C, within polymerization time is 7h, compares
In other initiators, the half-life of benzoyl peroxide is the most suitable, it is ensured that reach in the polymerization time related to
To preferable extent of polymerization, and owing to benzoyl peroxide belongs to low toxicity chemicals, use and store comparatively safe,
Therefore the preferred benzoyl peroxide of initiator described in manufacture method of the present invention.
Solvent described in manufacture method of the present invention be dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide,
One in toluene, dimethylbenzene, tetrachloroethylene.Compared with dimethyl acetylamide, dimethyl sulfoxide, dimethyl
Synthesized by the Methanamide dissolving present invention, the ability of polymer is the most prominent, and the polymer solution obtained contacts with water
Time, the speed that dimethylformamide enters water body is the most relatively fast, therefore is more beneficial for dynamic analysis of spinning solidified forming；
Compared with toluene, dimethylbenzene, tetrachloroethylene, the toxicity of dimethylformamide is minimum, for lower toxicity product, and
Other solvents are middle high toxicity product, for these reasons, and the preferred diformazan of solvent described in manufacture method of the present invention
Base Methanamide.
Water soluble alkali described in manufacture method of the present invention is sodium hydroxide, Lithium hydrate, potassium hydroxide, hydroxide
One in barium.Compared with Lithium hydrate, potassium hydroxide, sodium hydroxide is cheap, be easy to get, more conducively work
Industry is implemented；Compared with barium hydroxide, in doughnut last handling process, though sodium hydroxide and two in air
Carbon dioxide reaction, but product is water miscible, is difficult to remain on the hollow fibers, and barium hydroxide and air
The product of middle carbon dioxide reaction is but insoluble in water, easily remains on the hollow fibers, to its follow-up should
With impacting, based on above-mentioned two aspect reasons, the preferred hydroxide of water soluble alkali described in manufacture method of the present invention
Sodium.
Specific embodiment is given below, so that the present invention to be described in further detail, but the application claim protection model
Enclose and do not limited by specific embodiment.
Embodiment 1
Weigh two parts of 10g hydroxyethyl methylacrylates, be respectively placed in beaker a, in b, weigh 30g first
Base n-butyl acrylate, and be poured in above-mentioned beaker a, weigh 0.2g benzoyl peroxide, and by it
Join in above-mentioned beaker a, weigh 0.05g benzoyl peroxide, add it to, in above-mentioned beaker b, open
Opening magnetic agitation, until beaker a, the benzoyl peroxide in b is completely dissolved, and hereafter, weighs 50g diformazan
Base Methanamide, joins in above-mentioned beaker a, opens magnetic agitation, makes the material mix homogeneously in beaker a,
Subsequently solution in beaker a is poured in polymeric kettle, be passed through nitrogen with the air of residual in emptying polymeric kettle, unlatching
Polymeric kettle heating system, is warming up to 85 DEG C, now will contain the hydroxyethyl methylacrylate of initiator in beaker b
Progressively being added drop-wise in polymeric kettle, time for adding is 0.5h, after completion of dropwise addition, continues reaction 2h, and reaction terminates
After, move to resulting polymers solution A, in suitable beaker, seal standby；Replace with n-butyl acrylate
Above-mentioned n-BMA, repeats above-mentioned experiment, after reaction terminates, obtains polymer solution B, by it
It is placed in suitable beaker, seals standby；Take 34ml above-mentioned resulting polymers solution A, be placed in suitable beaker
In, take 6ml above-mentioned polymer solution B, be also added in above-mentioned beaker, magnetic agitation 1h, in order to mixing
Uniformly, the solution of mix homogeneously is poured into wet spinning and contains in liquid device, subsequently Sheng liquid device is placed in vacuum drying
Deaeration under the conditions of 40 DEG C and-0.1MPa in machine, the time is 30min, by peristaltic pump, mixed solution is fixed
Amount is transported in spinning pack, and quantitative transporting velocity is 0.6ml/min, forms hollow and spin after spinneret orifice is extruded
Silk thread, hollow dynamic analysis of spinning outer surface contacts with the coagulator in coagulating bath, additionally, will be solidifying by peristaltic pump
Gu agent is transported to inside hollow dynamic analysis of spinning so that it is contact with hollow dynamic analysis of spinning inner surface, conveying coagulator
Speed is 0.9ml/min, and coagulator is made up of deionized water, and under double diffusion effect, hollow dynamic analysis of spinning is solid
Turn to doughnut, doughnut be washed once in deionized water above, be placed in air dry oven,
Under the conditions of 50 DEG C, it is dried 1h, prepares nascent doughnut；Weigh 3.95g potassium permanganate, be placed on rule
Lattice are in the volumetric flask of 250ml, add deionized water subsequently in above-mentioned volumetric flask, and configuration concentration is
The potassium permanganate solution of 0.1mol/L, measures the above-mentioned potassium permanganate solution of 90ml, is placed on suitable burning
In Bei, weigh 10g sodium hydroxide, and add it in above-mentioned beaker, open magnetic agitation, make hydroxide
Sodium is completely dissolved, and prepares the mixed solution being made up of potassium permanganate, deionized water, sodium hydroxide, weighs 100g
Above-mentioned mixed solution, is placed in treatment trough, weighs 10g and comes into being doughnut, puts it in treatment trough,
It is immersed in mixed solution, treatment trough temperature is increased to 80 DEG C, start timing, nascent doughnut is entered
Row post processing, the process time is 30min, after post processing terminates, is taken out by nascent doughnut, uses deionization
Water cyclic washing, until no longer there being black particle thing to fall, is placed in air dry oven by nascent doughnut subsequently
In, under the conditions of 30 DEG C, it is dried 1h, preparing can be in the catalytic oxidant multiple dyestuff of rapidly and efficiently oxidation Decomposition
Hollow fiber.
Take the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue dyestuff is 23.28%；By 0.1g
Above-mentioned doughnut is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue is up to 97.36%.
Take the gorgeous blue aqueous solution of alkalescence that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of the gorgeous blue dyestuff of alkalescence is 4.26%；By on 0.1g
State doughnut to be placed in the gorgeous blue aqueous solution of alkalescence that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of alkaline gorgeous orchid is up to 85.43%.
Take the aqueous solution of methylene blue that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of methylene blue dye is 0.12%；By on 0.1g
State doughnut to be placed in the aqueous solution of methylene blue that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of methylene blue is up to 83.29%.
Take the Titration orchid aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of Titration orchid dyestuff is 3.33%；By 0.1g
Above-mentioned doughnut is placed in the Titration orchid aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml dioxygen
Water, is passed through 1min ozone, under the conditions of magnetic agitation, the clearance that after 90min, Titration is blue up to
78.91%.
Take the cationic brilliant red aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of Titration red is 3.07%；By 0.1g
Above-mentioned doughnut is placed in the cationic brilliant red aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml dioxygen
Water, is passed through 1min ozone, under the conditions of magnetic agitation, after 90min the clearance of cationic brilliant red up to
83.92%.
Take the cation kingfisher orchid aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of cation kingfisher orchid dyestuff is 1.36%；By 0.1g
Above-mentioned doughnut is placed in the cation kingfisher orchid aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml dioxygen
Water, is passed through 1min ozone, under the conditions of magnetic agitation, the clearance that after 90min, cation kingfisher is blue up to
61.24%.
Take the gorgeous blue aqueous solution of weak acid that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of the gorgeous blue dyestuff of weak acid is 20.89%；By 0.1g
Above-mentioned doughnut is placed in the gorgeous blue aqueous solution of weak acid that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of the gorgeous orchid of weak acid is up to 46.89%.
Take the acid lake blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of acid lake blue dyestuff is 2.09%；By on 0.1g
State doughnut to be placed in the acid lake blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of acid lake blue is up to 31.73%.
Embodiment 2
Only by the 34ml in embodiment 1, the volume that polymer solution A measures being adjusted to 36ml, polymer is molten
The volume that liquid B measures is adjusted to 4ml by by the 6ml in embodiment 1, other technical processs and parameter and enforcement
Example 1 is identical.
Learnt by embodiment 1 test result, under doughnut is catalyzed, hydrogen peroxide and ozone oxidation decompose sun from
The ability of son indigo plant is the strongest, and therefore, the present embodiment and subsequent embodiment are all carried out with cationic blue for model dyestuff
Catalytic performance characterizes.
Take the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue dyestuff is 23.28%；By 0.1g
Above-mentioned doughnut is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue is up to 82.37%.
Embodiment 3
Only by the 34ml in embodiment 1, the volume that polymer solution A measures being adjusted to 32ml, polymer is molten
The volume that liquid B measures is adjusted to 8ml by by the 6ml in embodiment 1, other technical processs and parameter and enforcement
Example 1 is identical.
Take the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue dyestuff is 23.28%；By 0.1g
Above-mentioned doughnut is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue is up to 94.23%.
Embodiment 4
Only by the 34ml in embodiment 1, the volume that polymer solution A measures being adjusted to 30ml, polymer is molten
The volume that liquid B measures is adjusted to 10ml by by the 6ml in embodiment 1, other technical processs and parameter and reality
Execute example 1 identical.
Take the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue dyestuff is 23.28%；By 0.1g
Above-mentioned doughnut is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue is up to 95.44%.
Embodiment 5
Only by the 34ml in embodiment 1, the volume that polymer solution A measures being adjusted to 28ml, polymer is molten
The volume that liquid B measures is adjusted to 12ml by by the 6ml in embodiment 1, other technical processs and parameter and reality
Execute example 1 identical.
Take the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue dyestuff is 23.28%；By 0.1g
Above-mentioned doughnut is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue is up to 97.58%.
Embodiment 6
Only by the 34ml in embodiment 1, the volume that polymer solution A measures being adjusted to 20ml, polymer is molten
The volume that liquid B measures is adjusted to 20ml by by the 6ml in embodiment 1, other technical processs and parameter and reality
Execute example 1 identical.
Take the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue dyestuff is 23.28%；By 0.1g
Above-mentioned doughnut is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue is up to 95.69%.
Embodiment 7
Only by the 34ml in embodiment 1, the volume that polymer solution A measures being adjusted to 40ml, polymer is molten
The volume that liquid B measures is adjusted to 0ml by by the 6ml in embodiment 1, other technical processs and parameter and enforcement
Example 1 is identical.
Take the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min
Ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue dyestuff is 23.28%；By 0.1g
Above-mentioned doughnut is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide,
Being passed through 1min ozone, under the conditions of magnetic agitation, after 90min, the clearance of cationic blue is up to 84.44%.
Claims (5)
1. the manufacture method being catalyzed oxidation Decomposition dyestuff doughnut, it is characterised in that technical process is as follows:
(1) solution polymerization process: weigh the quality monomers 1 such as two parts, be placed on suitable beaker a respectively, b
In, weighing monomer 2, the ratio making the 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 in above-mentioned a beaker, weigh initiator, making initiator quality is monomer 1 He in beaker a
The 0.2～2% of monomer 2 gross mass, and initiator is added beaker a, again weigh initiator, cause specifically
Agent quality is in beaker b the 0.2～2% of monomer 1 mass, and adds beaker b, opens magnetic agitation, until
Beaker a, in b, initiator is completely dissolved, and weighs solvent, makes solvent and two parts of monomers 1 and the total matter of monomer 2
The ratio of amount is 1: 5～5: 1, and is joined by solvent in above-mentioned beaker a, opens magnetic agitation, makes in beaker a
Material mix homogeneously, pours in polymeric kettle by solution in beaker a subsequently, is passed through nitrogen with residual in emptying polymeric kettle
Leave a blank gas, open polymeric kettle heating system, be warming up to 50～100 DEG C, now will be containing initiator in beaker b
Monomer 1 is progressively added drop-wise in polymeric kettle, and time for adding controls, within 10～60min, after completion of dropwise addition, to continue
Continuous reaction 2～6h, obtains polymer solution A, resulting polymers solution A is moved in suitable beaker, seals
Standby, change above-mentioned monomer 2 into monomer 3, obtain polymer solution B, and seal standby；
Described monomer 1 is hydroxyethyl methylacrylate, 2-(Acryloyloxy)ethanol, Hydroxypropyl methacrylate, propylene
One in acid hydroxypropyl fat, described monomer 2 is methyl methacrylate, ethyl methacrylate, metering system
Propyl propionate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, metering system
The most own ester of acid, n octyl methacrylate, 2-Propenoic acid, 2-methyl-, isooctyl ester, isodecyl methacrylate, methyl-prop
In alkene dodecyl gallate, tetradecyl methylacrylate, hexadecyl metrhacrylate, octadecyl methacrylate one
Kind, described monomer 3 is acrylic acid methyl ester., ethyl acrylate, propyl acrylate, n-butyl acrylate, propylene
Acid isobutyl ester, tert-butyl acrylate, the most own ester of acrylic acid, acrylic acid 1 Octyl Nitrite, acrylic acid are the most pungent
Ester, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, acrylic acid 16
One in ester, octadecyl acrylate；
(2) wet spinning technology: with volume ratio be by above-mentioned steps (1) resulting polymers solution A, B
99.99: 0.01～0.01: 99.99 mixes, and by mixture magnetic agitation 1～3h, in order to mix homogeneously,
Gained mixed solution is poured into wet spinning contain in liquid device, subsequently Sheng liquid device is placed in vacuum drier
Deaeration under the conditions of 25～95 DEG C and-0.07～-0.1MPa, the time is 0～60min, will be mixed by peristaltic pump
Closing solution to be quantitatively transported in spinning pack, quantitative transporting velocity is 0.2～2ml/min, after spinneret orifice is extruded
Forming hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface contacts with the coagulator in coagulating bath, additionally, pass through
Coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump so that it is contact with hollow dynamic analysis of spinning inner surface, defeated
The speed sending coagulator is 0.5～5ml/min, and coagulator is made up of deionized water and solvent, deionized water and molten
The mass ratio of agent is 10: 0～5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is cured as doughnut,
Doughnut be washed once in deionized water above, be placed in air dry oven, at 25～50 DEG C of bars
It is dried 1～6h under part, prepares nascent doughnut；
(3) aftertreatment technology: weigh the potassium permanganate of certain mass, is placed in volumetric flask, adds one
Determining volumes of deionized water, configuration concentration is the potassium permanganate solution of 0.01～10mol/L, measures certain volume
Above-mentioned potassium permanganate solution, is placed in suitable beaker, weighs the water soluble alkali of certain mass, makes solvable
The property quality of alkali is 1: 5～1: 20 with the ratio of the volume of potassium permanganate solution, and is joined by water soluble alkali
State in beaker, open magnetic agitation, make water soluble alkali be completely dissolved, prepare by potassium permanganate, deionized water,
The mixed solution of water soluble alkali composition, weighs the above-mentioned mixed solution of certain mass, is placed in treatment trough,
Weigh the nascent doughnut of certain mass, make the nascent doughnut with above-mentioned mixed solution mass ratio be
1: 5～1: 50, and nascent doughnut is placed in treatment trough so that it is it is immersed in mixed solution, by treatment trough
Temperature is increased to 25～95 DEG C, starts timing, nascent doughnut is carried out post processing, and finishing time is
5min～6h, after post processing terminates, takes out nascent doughnut, uses deionized water cyclic washing, until not
There is black particle thing to fall again, subsequently nascent doughnut is placed in air dry oven, at 25～50 DEG C of bars
Being dried 1～6h under part, preparing can the doughnut of the catalytic oxidant multiple dyestuff of rapidly and efficiently oxidation Decomposition.
A kind of manufacture method being catalyzed oxidation Decomposition dyestuff doughnut the most according to claim 1, its
The initiator being characterised by described is benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, tertiary fourth
One in base hydrogen peroxide, cumyl peroxide, di-t-butyl peroxide.
A kind of manufacture method being catalyzed oxidation Decomposition dyestuff doughnut the most according to claim 1, its
The solvent being characterised by described is dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide, toluene, diformazan
One in benzene, tetrachloroethylene.
A kind of manufacture method being catalyzed oxidation Decomposition dyestuff doughnut the most according to claim 1, its
The water soluble alkali being characterised by described is the one in sodium hydroxide, Lithium hydrate, potassium hydroxide, barium hydroxide.
5. according to a kind of system being catalyzed oxidation Decomposition dyestuff doughnut according to any one of Claims 1 to 4
Making method, it is characterised in that described monomer 1 is hydroxyethyl methylacrylate, described monomer 2 is methyl-prop
Olefin(e) acid N-butyl, described monomer 3 is n-butyl acrylate, and described initiator is benzoyl peroxide, institute
The solvent stated is dimethylformamide, and described water soluble alkali is sodium hydroxide.
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| CN107245771A (en) * | 2017-06-29 | 2017-10-13 | 天津工业大学 | A kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst |
| CN107308988A (en) * | 2017-06-29 | 2017-11-03 | 天津工业大学 | A kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst |
| CN110767883A (en) * | 2019-07-02 | 2020-02-07 | 罗宝林 | Modified fiber, preparation method and application |
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