CN107308938B - A kind of manufacturing method of threadiness heterogeneous Fenton catalyst - Google Patents
A kind of manufacturing method of threadiness heterogeneous Fenton catalyst Download PDFInfo
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- CN107308938B CN107308938B CN201710530870.3A CN201710530870A CN107308938B CN 107308938 B CN107308938 B CN 107308938B CN 201710530870 A CN201710530870 A CN 201710530870A CN 107308938 B CN107308938 B CN 107308938B
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- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- 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
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- 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
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- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- 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
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- 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
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- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- 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
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- 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
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Abstract
The invention discloses the design of functional fibre material in textile material field and manufactures, be related to a kind of preparation of fibrous heterogeneous Fenton catalyst, specially one kind can catalytic oxidant (such as hydrogen peroxide, ozone) quickly, efficient oxidation decompose a variety of dyestuffs, the reusable, manufacturing method of fiber that is easy to separate with water body.Technologies, the gained fibers such as the manufacturing method integrated use precipitation polymerization, wet spinning, penetrating power promotion, iron ion complexing, heat cross-linking can be used for the processing of the water bodys containing organic matter such as waste water from dyestuff.Gained fiber is compared with existing heterogeneous Fenton catalyst, it is more preferable to the treatment effect of the water bodys containing organic matter such as waste water from dyestuff, compared with the Fenton catalysts made from the same type wet spinning process fiber, the Speed Efficient oxygenolysis organic matter that can be exceedingly fast, realize quick, effective purification to water body, while reusability significantly improves, application cost reduces, therefore, more meet industrial applicibility requirement.
Description
Technical field
The invention belongs to the design of functional fibre material in textile material field and manufactures, are related to a kind of fibrous out-phase
The preparation of Fenton catalysts, specially one kind can catalytic oxidant (such as hydrogen peroxide, ozone) quickly, efficient oxidation
Decompose a variety of dyestuffs, the reusable, manufacturing method of fiber that is easy to separate with water body.The manufacturing method integrated use is heavy
Technologies, the gained fibers such as shallow lake polymerization, wet spinning, penetrating power promotion, iron ion complexing, heat cross-linking can be used for waste water from dyestuff etc.
The processing of the water body containing organic matter.
Background technique
It is constantly progressive with the rapid development of society with industrial, the water pollution problems being on the rise is to the existence of the mankind
Safety constitutes significant threat, becomes the major obstacles of human health, economy and society sustainable development.And textile printing and dyeing industry is made
For typical highly water intensive industry, production process process is sufficiently complex, need to consume nearly hundred million tons of water every year, thus generate a large amount of dyestuff
Waste water causes serious environmental problem.(Guangwei Zhang, Idzumi Okajima, Takeshi Sako,
Decomposition and decoloration of dyeing wastewater by hydrothermal
Oxidation, The Journal of Supercritical Fluids, 2016,112 (1): 136-142；Terinte N,
Manda B M K, Taylor J, et al, Environmental assessment of coloured fabrics and
Opportunities for value creation:Spin-dyeing versus conventional dyeing of
Modal fabrics, Journal of Cleaner Production, 2014,72 (6): 127-138).Waste water from dyestuff at
It is point sufficiently complex, have the characteristics that water is big, change of water quality is big, high organic content, coloration height, biodegradability are poor, and contain more
Organic matter with bio-toxicity or " three cause property " (carcinogenic, teratogenesis and mutagenicity), direct emission can bring living environment
High risks, while the waste of water resource is caused, and as state and society is to the pay attention to day by day of environmental protection requirement, it is traditional
Dye waste water treatment method have been unable to meet production and environmental protection requirement, therefore, at present dye wastewater treatment field there is an urgent need to
Seek efficient, inexpensive processing material and technology (Ay F, Catalkaya E C, Kargi F, A statistical
experiment design approach for advanced oxidation of Direct Red azo-dye by
Photo-Fenton treatment, 2009,162 (1): 230-236).
Since the 1980s, countries in the world environmental science and technology has been caused to generate the high-level oxidation technology that OH is mark
The attention on boundary, due to high-level oxidation technology have the characteristics that oxidability by force and it is without secondary pollution, so be considered as processing water
Middle hardly degraded organic substance most has the technology of application prospect.Compared with other high-level oxidation technologies, Fenton method is due to having reaction
Rapidly, oxidability is strong, good decolorizing effect and the features such as strong flexibility, it is considered to be is widely used at present and with development potential
One of dye waste water treatment method.Fenton system passes through Fe2+With H2O2Reaction generates the OH with high reaction activity,
And OH has the Strong oxdiative ability for being only second to fluorine, can be produced with oxygenolysis organic pollutant, intermediate as oxidation process
Object can induce subsequent chain reaction, and the substance of certain difficult for biological degradation is made to be transformed into the substance of easy biological treatment, and
The chromogenic or auxochrome group for destroying dyestuff, makes it lose color development ability, so that coloring matter is made to degrade, organic pollutant is thorough
It is harmless to turn to carbon dioxide and water.Chemical reaction condition needed for Fenton system is mild, easy to accomplish, and oxidation reaction does not have
Have introduce other poisonous and harmful substances, for waste water from dyestuff improvement open new approach (Ayoub K, N é lieu S,
Hullebusch E D V, et al., TNT oxidation by Fenton reaction:Reagent ratio effect
On kinetics and early stage degradation pathways, Chemical Engineering
Journal, 2011,173 (2): 309-317).
Currently, Fenton reaction system mainly includes the homogeneous and big reaction system of out-phase two, to further increase organic matter
Removal effect, by optics, ultrasonic technology and electrochemical techniques etc. be dissolved into Fenton reaction in form novel homogeneous
Fenton reaction system (Babuponnusami A, Muthukumar K, A review on Fenton and
Improvements to the Fenton process for wastewater treatment, Journal of
Environmental Chemical Engineering, 2014,2 (1): 557-572；Han Z, Dong Y, Dong S,
Copper-iron bimetal modified PAN fiber complexes as novel heterogeneous
Fenton catalysts for degradation of organic dye under visible light
Irradiation, Journal of Hazardous Materials, 2011,189 (1-2): 241-248), but it is common homogeneous
Fenton reaction system is still that Fenton method processing dyestuff is useless with the absolute predominance in terms of cost and technical feasibility
Common reaction system when water.But for common homogeneous Fenton reaction system, because its only at lower pH
It can be effectively carried out, need to adjust waste water repeatedly pH value to acidity, increase processing cost, and homogeneous Fenton reaction system
Catalyst it is miscible in waste water in the form of an ion, homogeneous catalyst and reactant, reaction product mixing, cause using rear catalysis
Agent is difficult to separate, and generates a large amount of iron cements, and post-processing is complicated, waste reaction resource, and improves use cost, limits homogeneous
The application of Fenton reaction system.
With in Fenton reaction system catalyst research deeply and the enhancing of mankind's environmental consciousness, by divalent or
Ferric ion, other ions and compound ion are supported on certain carrier, form heterogeneous Fenton catalyst, different
Phase Fenton reaction system can handle waste water from dyestuff within the scope of wide pH, i.e., organic molecule is adsorbed onto catalyst table first
Face, in active component and H2O2Under the action of, organic molecule decomposes, and the product desorption after degradation simultaneously returns in solution, in turn
Pollutant process is completed, and heterogeneous Fenton catalyst can be separated with aqueous systems easily, and then can be repeatedly used, In
During this, since the iron ion amount of elution is few, therefore a large amount of iron cements (Zeng X, Lemley A T, Fenton will not be generated
Degradation of 4,6-Dinitro-o-cresol with Fe2+- Substituted Ion-Exchange Resin,
Journal of Agricultural&Food Chemistry, 2009,57 (9): 3689-3694).It follows that out-phase
Fenton reaction system had not only remained the advantages of homogeneous Fenton reaction, but also significantly compensated for its deficiency, was greatly simplifying processing
On process base, it can greatly expand wastewater treatment range, it has also become an important development of Fenton method processing organic wastewater
Direction will also play a positive role in the treatment of waste water, have fabulous application prospect.
Currently, heterophase Fenton catalyst mainly includes load typed iron catalyst, iron powder or iron ore catalyst etc..Load
Sections catalyst can preferably solve the secondary pollution problems of iron ion in homogeneous Fenton system, and carrier is either have
Airborne body, is also possible to inorganic carrier, and Nafion membrane is a kind of cation exchange being made of perfluorinated sulfonic acid anionic polymer
Film has many advantages, such as that heat-resisting, corrosion-resistant and intensity is high, but since Nafion membrane is expensive, also needs to consider film in practical application
Oxidation resistance and (Wu Wei, Wu Chengcheng, Zhao Yaping, heterogeneous Fenton technology degradable organic pollutant the problems such as fouling membrane
Progress, Environmental science and technology, 2010,06:99-104)；In addition, some macromolecular organic compounds such as sodium alginate
Deng also can be used as immobilization carrier (Cruz A, Couto L, Esplugas S, et al., Study of the
contribution of homogeneous catalysis on heterogeneous Fe(III)/alginate
Mediated photo-Fenton process, Chemical Engineering Journal, 2016,318:272-280),
But such carrier is difficult to be subjected to the oxidation corrosion of OH.In inorganic material, aluminium oxide is a kind of common catalyst carrier, molecule
Sieve be also commonly used as catalyst carrier (Zhou Yaliang, Huang Dongyue, the type and progress of Fenton's reaction technology, Guangdong chemical industry,
2013,40 (1): 74-74)；Clay, main component are kaolin, frequently as iron ion carrier (Li Huanyu, it is heterogeneous
The progress of Fenton reaction treatment organic pollutant, building and budget, 2015,06:47-50), using inorganic material as carrier
Heterogeneous Fenton catalyst there is at low cost, the advantages such as specific surface area height and adsorption capacity are strong, but catalyst preparation mistake
Journey is complicated, and fine catalyst is difficult to recycle, and application is restricted.Iron powder or iron ore catalyst are primarily present in nature ore
In, magnetic material has magnetic iron ore, maghemite, perovskite, lepidocrocite and spinelle etc., and non-magnetic material has bloodstone and needle iron
Mine etc., iron powder and these mineral materials itself can be with H2O2Constitute Fenton system come degradation of organic substances (Khataee A,
Taseidifar M, Khorram S, et al., Preparation of nanostructured magnetite with
plasmafor degradation of a cationic textile dye by the heterogeneous Fenton
Process, Journal of the Taiwan Institute of Chemical Engineers, 2015,53:132-
139；Munoz M, Pedro Z M D, Casas J A, et al., Preparation of magnetite-based
Catalysts and their application in heterogeneous Fenton oxidation-A review,
Applied Catalysis B Environmental, 2015,176:249-265), but ferriferous oxide Fenton reaction system
It is affected by pH, in acid condition, the dissolution of iron ion can induce H2O2OH is generated, but the iron ion dissolved out is eventually given birth to
At iron cement, cause secondary pollution, and ore iron type is less and limited source, limit it and further apply.
In the above context, novel carriers material is researched and developed, keeps iron ion or iron oxide securely and equal
It loads evenly on it, is easily isolated solid-liquid while improving catalytic performance；On the other hand, in the same of selection suitable carrier
When iron species are modified, be made excellent combination property heterogeneous Fenton catalyst, become great real value.
The present invention selects suitable polymerized monomer first, using precipitation polymerization method synthesis rich in the poly- of specific functional groups carboxyl, hydroxyl etc.
Object is closed, then the polymer of synthesis is dissolved in water soluble alkali aqueous solution, using this solution as spinning solution, with inorganic acid aqueous solution
It for setting medium, using wet spinning technology spinning fibre, and is handled through special process, after assigning loose and porous structure to forming
Fiber, to reduce osmotic resistance when iron ion adsorbs and fixes, thus make within the limited time fibrous inside be full of iron from
Son, iron ion load capacity increase, through thermal crosslinking treatment after, make to be dehydrated between amount of activated group carboxyl and hydroxyl and form friendship
Join network structure, cross-linked network structure fetter iron ion, along between carboxyl, hydroxyl and iron ion strong complexing and
The constraint of fiber surface acts on, and is securely joined with iron ion more in fibrous inside, iron ion washes when greatly reducing application
De- amount assigns finished fiber fabulous reusability, becomes heterogeneous Fenton catalyst truly, together
When in thermal crosslinking treatment, selected using atmosphere in high temperature furnace, realize and the existence form, form, crystal form of iron species are carried out
Modification, further enhances its catalytic activity, to the processing for water bodys containing organic matter such as waste water from dyestuff, for reaching for above-mentioned water body
New processing material is developed in mark discharge.
Summary of the invention
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is to provide a kind of fibrous heterophase Fenton
The manufacturing method of catalysts.The manufacturing method selects suitable monomer on the basis of prior art invention first, using heavy
Polymer of the polymerization synthesis in shallow lake rich in specific functional groups carboxyl, hydroxyl etc., then dissolves a polymer in water soluble alkali aqueous solution
In, using this solution as spinning solution, using inorganic acid aqueous solution as setting medium, using wet spinning technology spinning fibre, then pass through
Special process processing, assigns loose and porous structure to fiber, in soluble ferrite aqueous solution, since loose and porous structure draws
The hyposmosis resistance of hair, iron ion quickly enters fibrous inside by solution, and is complexed with carboxyl, hydroxyl, adds fiber surface
Constraint, so that iron ion is firmly fixed at fibrous inside, after thermal crosslinking treatment, be dehydrated and shape between part carboxyl and hydroxyl
At cross-linked network structure, it is securely joined with iron ion more in fibrous inside, iron ion is not easy to be eluted, and fiber is provided with different
Phase Fenton catalytic reaction function.Gained fiber is compared with conventional Fenton catalysts, except the few, H with fiber consumption2O2
Outside the advantages that organic removal rates such as consumption is low, pH is applied widely, dyestuff are high, removal speed is fast, also having can be non-woven
Or textile process, easy to use, the advantages that can recycling easily, more meet the requirement of industrial applicibility.
The technical solution that the present invention solves the technical problem is: designing a kind of fibrous heterogeneous Fenton catalyst
Manufacturing method, technical process is as follows:
(1) Precipitation Polymerization Process: weighing two parts of monomers 1, places it in suitable beaker a, b, makes in beaker a respectively
1 mass ratio of monomer in monomer 1 and beaker b is 10: 0~0: 10, does not include two endpoints, weighs the monomer 2 of certain mass,
Making the ratio between gross mass of monomer 2 and two parts of monomers 1 is 0: 10~4: 6, does not include 0: 10, and monomer 2 is poured into above-mentioned beaker a
In, the initiator of certain mass is weighed, 0.2~2% of 2 gross mass of monomer 1 and monomer in initiator quality beaker a is made, and
It adds it in above-mentioned beaker a, stirring is dissolved completely in monomer up to initiator, is weighed initiator again, is made initiator
Quality is 0.2~2% of 1 mass of monomer in above-mentioned beaker b, and is added to above-mentioned beaker b, and stirring is until initiator is completely dissolved
In monomer, appropriate amount of deionized water is weighed, making the ratio between itself and 2 gross mass of monomer 1 and monomer is 1: 2~2: 1, and it is slowly added
Enter into above-mentioned beaker a, stirring is uniformly mixed the liquid in beaker a, and then mixed system is transferred in polymeric kettle, is passed through
Nitrogen opens stirring to empty remaining air in polymeric kettle, opens polymeric kettle heating system, fluid temperature liter in kettle to be polymerized
At up to 70~95 DEG C, the monomer 1 in beaker b containing initiator is added drop-wise in polymeric kettle dropwise, time for adding control 10~
Within 60min, after completion of dropwise addition, the reaction was continued 1~4h takes out gum-like product, is washed with deionized more than once, removes not
The monomer and oligomer of reaction, in vacuum drier under the conditions of 40~80 DEG C after dry 48~96h, in high speed disintegrator
It is fully ground, polymer powder is made, and seal spare；
The monomer 1 is one of acrylic acid, methacrylic acid, maleic anhydride；
The monomer 2 is one of hydroxyethyl methacrylate, hydroxy propyl methacrylate；
The initiator be benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide,
One of cumyl peroxide, di-t-butyl peroxide；
(2) wet spinning technology: weighing certain mass deionized water, places it in suitable beaker, weighs certain matter
Water soluble alkali is measured, makes the mass ratio 0.0001: 9.9999~9.5000: 0.5000 of water soluble alkali and deionized water, by it
It is added in the above-mentioned beaker containing deionized water, solvent is made after water soluble alkali is completely dissolved；Weigh certain mass step
(1) polymer powder obtained in makes the mass ratio 0.1: 10~3: 10 of polymer Yu above-mentioned solvent, polymer is added
Into the above-mentioned beaker containing solvent, magnetic agitation is carried out at 40~80 DEG C and is stopped after object to be polymerized is dissolved completely in solvent
It only stirs and is cooled to room temperature, spinning solution is made；The deionized water for measuring certain volume, places it in coagulating bath, measures
The inorganic acid of certain volume, making the ratio between volume of inorganic acid and deionized water is 0.2: 9.8~9.8: 0.2, it is slowly fallen
Enter in above-mentioned coagulating bath, stirring is uniformly mixed deionized water and inorganic acid, and setting medium is made in cooled to room temperature；It will gather
Tetrafluoroethene spinning pack is immersed in setting medium, is driven above-mentioned spinning solution to polytetrafluoroethylene (PTFE) spinneret using peristaltic pump
In component, to form dynamic analysis of spinning, dynamic analysis of spinning is frozen into silk in coagulating bath, sufficiently after drying, can be obtained and is attached with nothing
The fiber of machine hydrochlorate；
The inorganic acid is one of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid；
The water soluble alkali is one of sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide；
(3) specially treated technique: A technique, it is attached to remove with fiber obtained in deionized water repeatedly washing step (2)
Washed fiber is immersed in one when the deionized water pH value of washed fiber is close to 7 in the inorganic acid salt of fiber surface
Determine in the deionized water of quality, be swollen fiber sufficiently in deionized water, above-mentioned swollen fiber is placed in vacuum freeze drying
Freezed, dried in equipment, condenser temperature be -80 DEG C~-40 DEG C, cooling time be 12~36h, vacuum degree be 0Pa~
100Pa, drying time are 12~36h, are sufficiently parched to fiber, and being made has loose and porous structure fiber；B technique, spend from
Sub- water fiber obtained in washing step (2) repeatedly, to remove the inorganic acid salt for being attached to fiber surface, when washed fiber
When deionized water pH value is close to 7, washed fiber is placed under natural environment dry 24~96h, weigh certain mass go from
Sub- water places it in suitable beaker, then weighs a certain amount of water soluble alkali, and water soluble alkali is added to above-mentioned deionized water
In, stirring to water soluble alkali is completely dissolved, and the water soluble alkali aqueous solution that mass percent concentration is 0.01%~3% is made, will
The fiber of natural air drying is immersed in water soluble alkali aqueous solution, so that fiber is sufficiently swollen, is then washed repeatedly with deionized water
Fiber, until the deionized water pH value of washed fiber is close to 7, being made has loose and porous structure fiber；
The water soluble alkali is one of sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide；
(4) complexing technique: weighing certain mass deionized water, places it in suitable beaker, then weighs and deionized water
The soluble ferrite that mass ratio is 0: 10~10: 0 does not include two endpoints, adds it in above-mentioned deionized water, stirring
It is completely dissolved to soluble ferrite；Fiber obtained in step (3) is taken, fiber and above-mentioned soluble ferrite aqueous solution matter are made
The ratio between amount is 0: 10~10: 10, does not include 0: 10, and fiber is immersed in soluble ferrite aqueous solution, at 20~80 DEG C
Under fiber is complexed with iron ion, be complexed several seconds~300min after, fiber is taken out from perferrite solution immediately, is obtained
There is the fiber of ferrous ion to complexing；
The soluble ferrite is one of frerrous chloride, ferrous sulfate, ferrous nitrate；
(5) heat cross-linking technique: the fiber that the complexing that step (4) obtain has ferrous ion is placed in high temperature furnace and carries out hot friendship
Connection, high temperature furnace temperature are 100~300 DEG C, and crosslinking time is 5~80min, and atmosphere can be air, nitrogen and helium in high temperature furnace
Fiber is then taken out from high temperature furnace, is cooled in the natural environment by the inert gases such as gas, neon, argon gas, nitrogen, xenon
Threadiness heterogeneous Fenton catalyst is made in room temperature.
Compared with prior art products, firstly, present invention gained fiber morphologically has outstanding advantage, it is at this stage, different
Phase Fenton catalysts are mostly powdered or graininess, and form is single and preparation process is many and diverse, need to be by mistake after
The means separating catalysts such as filter, centrifugation, otherwise catalyst easily remains in water and causes secondary pollution, and application cost significantly mentions
It rises, present invention gained fiber can directly be launched completion pair in waste water when handling the water bodys containing organic matter such as waste water from dyestuff
The processing of waste water can recycle easily after, be not easy to cause secondary pollution to environment, be dried, be used multiple times, and pole
The earth reduces use cost, and can through weaving or it is non-woven be processed into variform product, be able to satisfy different application neck
Demand of the domain to form；Secondly, present invention gained fiber is extremely hydrophilic, large specific surface area, and active specy iron ion is in fiber
Part dissipates extremely uniformly, therefore with after waste water containing organic matter, it is acted in hydrophilic bigger serface, the active specy that is uniformly dispersed
Under, compared with existing heterogeneous Fenton catalyst, the treatment effect of water body containing organic matter is more preferable, in addition, with same type wet process
Fenton catalysts made from spin processes fiber are compared, and when ferrous ion is complexed, present invention gained fiber has loose
Porous structure can load more iron ions in a very short period of time, and the thermal crosslinking treatment then carried out is bound iron ion
In cross-linked network structure, simultaneously because the constraint of carboxyl, the strong complexing of hydroxyl and iron ion and fiber compact surfaces
Effect, iron ion are difficult to flee from fibrous inside, cause iron ion elution amount when application to drastically reduce, reusability significantly mentions
Height, since elution amount strongly reduces, fibrous inside has retained a large amount of iron ions, in the case of iron ion largely exists, can quickly urge
Change oxidant (such as hydrogen peroxide, ozone) and generates a large amount of OH isoreactivity oxygen species, and then efficient oxidation at a terrific speed
Decomposing organic matter realizes that quick, effective purification to water body regulates and controls in thermal crosslinking treatment through atmosphere in high temperature furnace, can be into one
Existence form, form, the crystal form etc. of step modification iron species, further enhance the catalytic activity of fiber, and application prospect is more prominent,
Finally, in the range of applicant's retrieval, there is not yet manufacturing fibrous heterogeneous Fenton using technique of the present invention
The pertinent literature of catalyst is reported.
Specific embodiment
Be further discussed below the present invention below with reference to embodiment: a kind of fibrous heterogeneous Fenton that the present invention designs is urged
The manufacturing method (hereinafter referred to as manufacturing method) of agent is related to precipitation polymerization, wet spinning, penetrating power promotion, iron ion network
The integrated application of the technologies such as conjunction, heat cross-linking, it is intended to iron when solving existing threadiness Fenton catalysts because of preparation
The caused reusability of the defects of iron ion is easily eluted when ion load low efficiency, application is poor and due to iron species are single
The problems such as caused catalytic activity is weak creates new material for water body treatings containing organic matter such as waste water from dyestuff, technical process or
Steps are as follows:
(1) Precipitation Polymerization Process: weighing two parts of monomers 1, places it in suitable beaker a, b, makes in beaker a respectively
1 mass ratio of monomer in monomer 1 and beaker b is 10: 0~0: 10, does not include two endpoints, weighs the monomer 2 of certain mass,
Making the ratio between gross mass of monomer 2 and two parts of monomers 1 is 0: 10~4: 6, does not include 0: 10, and monomer 2 is poured into above-mentioned beaker a
In, the initiator of certain mass is weighed, 0.2~2% of 2 gross mass of monomer 1 and monomer in initiator quality beaker a is made, and
It adds it in above-mentioned beaker a, stirring is dissolved completely in monomer up to initiator, is weighed initiator again, is made initiator
Quality is 0.2~2% of 1 mass of monomer in above-mentioned beaker b, and is added to above-mentioned beaker b, and stirring is until initiator is completely dissolved
In monomer, appropriate amount of deionized water is weighed, making the ratio between itself and 2 gross mass of monomer 1 and monomer is 1: 2~2: 1, and it is slowly added
Enter into above-mentioned beaker a, stirring is uniformly mixed the liquid in beaker a, and then mixed system is transferred in polymeric kettle, is passed through
Nitrogen opens stirring to empty remaining air in polymeric kettle, opens polymeric kettle heating system, fluid temperature liter in kettle to be polymerized
At up to 70~95 DEG C, the monomer 1 in beaker b containing initiator is added drop-wise in polymeric kettle dropwise, time for adding control 10~
Within 60min, after completion of dropwise addition, the reaction was continued 1~4h takes out gum-like product, is washed with deionized more than once, removes not
The monomer and oligomer of reaction, in vacuum drier under the conditions of 40~80 DEG C after dry 48~96h, in high speed disintegrator
It is fully ground, polymer powder is made, and seal spare；
(2) wet spinning technology: weighing certain mass deionized water, places it in suitable beaker, weighs certain matter
Water soluble alkali is measured, makes the mass ratio 0.0001: 9.9999~9.5000: 0.5000 of water soluble alkali and deionized water, by it
It is added in the above-mentioned beaker containing deionized water, solvent is made after water soluble alkali is completely dissolved；Weigh certain mass step
(1) polymer powder obtained in makes the mass ratio 0.1: 10~3: 10 of polymer Yu above-mentioned solvent, polymer is added
Into the above-mentioned beaker containing solvent, magnetic agitation is carried out at 40~80 DEG C and is stopped after object to be polymerized is dissolved completely in solvent
It only stirs and is cooled to room temperature, spinning solution is made；The deionized water for measuring certain volume, places it in coagulating bath, measures
The inorganic acid of certain volume, making the ratio between volume of inorganic acid and deionized water is 0.2: 9.8~9.8: 0.2, it is slowly fallen
Enter in above-mentioned coagulating bath, stirring is uniformly mixed deionized water and inorganic acid, and setting medium is made in cooled to room temperature；It will gather
Tetrafluoroethene spinning pack is immersed in setting medium, is driven above-mentioned spinning solution to polytetrafluoroethylene (PTFE) spinneret using peristaltic pump
In component, to form dynamic analysis of spinning, dynamic analysis of spinning is frozen into silk in coagulating bath, sufficiently after drying, can be obtained and is attached with nothing
The fiber of machine hydrochlorate；
(3) specially treated technique: A technique, it is attached to remove with fiber obtained in deionized water repeatedly washing step (2)
Washed fiber is immersed in one when the deionized water pH value of washed fiber is close to 7 in the inorganic acid salt of fiber surface
Determine in the deionized water of quality, be swollen fiber sufficiently in deionized water, above-mentioned swollen fiber is placed in vacuum freeze drying
Freezed, dried in equipment, condenser temperature be -80 DEG C~-40 DEG C, cooling time be 12~36h, vacuum degree be 0Pa~
100Pa, drying time are 12~36h, and thoroughly to fiber abundant thousand, being made has loose and porous structure fiber；B technique, spend from
Sub- water fiber obtained in washing step (2) repeatedly, to remove the inorganic acid salt for being attached to fiber surface, when washed fiber
When deionized water pH value is close to 7, washed fiber is placed under natural environment dry 24~96h, weigh certain mass go from
Sub- water places it in suitable beaker, then weighs a certain amount of water soluble alkali, and water soluble alkali is added to above-mentioned deionized water
In, stirring to water soluble alkali is completely dissolved, and the water soluble alkali aqueous solution that mass percent concentration is 0.01%~3% is made, will
The fiber of natural air drying is immersed in water soluble alkali aqueous solution, so that fiber is sufficiently swollen, is then washed repeatedly with deionized water
Fiber, until the deionized water pH value of washed fiber is close to 7, being made has loose and porous structure fiber；
(4) complexing technique: weighing certain mass deionized water, places it in suitable beaker, then weighs and deionized water
The soluble ferrite that mass ratio is 0: 10~10: 0 does not include two endpoints, adds it in above-mentioned deionized water, stirring
It is completely dissolved to soluble ferrite；Fiber obtained in step (3) is taken, fiber and above-mentioned soluble ferrite aqueous solution matter are made
The ratio between amount is 0: 10~10: 10, does not include 0: 10, and fiber is immersed in soluble ferrite aqueous solution, at 20~80 DEG C
Under fiber is complexed with iron ion, be complexed several seconds~300min after, fiber is taken out from perferrite solution immediately, is obtained
There is the fiber of ferrous ion to complexing；
(5) heat cross-linking technique: the fiber that the complexing that step (4) obtain has ferrous ion is placed in high temperature furnace and carries out hot friendship
Connection, high temperature furnace temperature are 100~300 DEG C, and crosslinking time is 5~80min, and atmosphere can be air, nitrogen and helium in high temperature furnace
Fiber is then taken out from high temperature furnace, is cooled in the natural environment by the inert gases such as gas, neon, argon gas, Krypton, xenon
Threadiness heterogeneous Fenton catalyst is made in room temperature.
Monomer 1 described in manufacturing method of the present invention be one of acrylic acid, methacrylic acid, maleic anhydride, by
The polymer that the polymerization of monomer 1 generates contains a large amount of carboxylic acid groups, can be ionized into electronegative carboxylate anion in water, so with Asia
Iron ion is complexed, and is securely joined with ferrous ion in fiber surface and inside, in addition, under high temperature action, carboxylic acid group
Between and carboxylic acid group and hydroxyl between can be dehydrated and assign cross-linked network structure to polymer macromolecule, therefore, the present invention manufacture
Monomer 1 described in method is
Heat cross-linking reaction is provided safeguard.The preferred acrylic acid of monomer 1 described in manufacturing method of the present invention, the reason is as follows that: 1. acrylic acid
It is the very fast vinyl monomer of simplest unsaturated carboxylic acid and polymerization speed；Meeting when 2. methacrylic acid is thermally decomposed
Toxic gas is generated, this gas can form explosive mixture with air；3. maleic anhydride has strong impulse smell, and
And it is toxic, skin and mucous membrane can be stimulated, hypopsia is caused even to be blinded when serious；Based on above-mentioned three aspects reason, the present invention
The preferred acrylic acid of monomer 1 described in manufacturing method.
Monomer 2 described in manufacturing method of the present invention be one of hydroxyethyl methacrylate, hydroxy propyl methacrylate,
Only polymerize with monomer 1, system viscosity can increased dramatically in polymerization process, in addition generate implode, it is difficult to obtain molecular weight and
Molecular weight distribution be suitable for can spinning polymerizate, even if obtaining the homopolymer of monomer 1, which is dissolved in water, but its water
Solution is difficult to solidify, and brings extreme difficulties to spinning technique, and 2 one side of monomer is the polymerization temperature for improving system as a result,
And degree, it is on the other hand the spinning spinnability for improving resulting polymers, in addition, monomer 2 contains active group hydroxyl, hydroxyl
Base and ferrous ion also have strong complexing, can be dehydrated under high temperature action, between hydroxyl and between carboxylic acid group and hydroxyl and incite somebody to action
Cross-linked network structure assigns polymer macromolecule, and therefore, fiber can be enhanced to the fix tightly of ferrous ion in the introducing of monomer 2
Degree, while also provide safeguard for heat cross-linking reaction.The preferred hydroxyethyl methacrylate of monomer 2 described in manufacturing method of the present invention
Ethyl ester, the reason is as follows that: compared with hydroxy propyl methacrylate, hydroxyethyl methacrylate has vinyl and hydroxyl, is a kind of
High activity contains monomer, and is nonpoisonous chemicla, is widely used as the medical materials such as dentistry, orthopaedics, contact lenses.
Initiator described in manufacturing method of the present invention be benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide,
One of tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide, 1. selecting the principle of initiator includes:
Half-life period initiator appropriate is selected according to polymerization temperature, keeps polymerization time moderate, based on the heat-transfer capability of polymeric kettle, In
Guarantee temperature control and under the premise of avoiding implode, should be used as much as possible the initiator of high activity, i.e. half-life period shorter initiation
Agent shortens polymerization time to improve rate of polymerization, while can reduce polymerization temperature and reduce initiator amount；2. should also examine
Consider initiator on polymer quality whether there is or not influence, initiator have in non-toxic, use and storage process whether security problems.It is many
Well known, half-life period of the di-t-butyl peroxide at 100 DEG C is 218h, half-life period of the cumyl peroxide at 115 DEG C
For 12.3h, half-life period of the tert-butyl hydroperoxide at 154.5 DEG C is 44.8h, isopropyl benzene hydroperoxide at 125 DEG C half
Phase of declining is 21h, and half-life period of the azodiisobutyronitrile at 100 DEG C is 0.1h, and half-life period of the benzoyl peroxide at 125 DEG C be
0.42h, and temperature reduces Increased Plasma Half-life, temperature increases half life.Polymeric reaction temperature range of the present invention is
70~95 DEG C, the time is 1~4h, and for above-mentioned temperature range and the reaction time of requirement, the half-life period of benzoyl peroxide is equal
It is more appropriate, it is ensured that ideal extent of polymerization to be reached in the polymerization time being related to, and due to benzoyl peroxide category
Less toxic chemicals, use and store it is comparatively safe, therefore currently preferred initiator be benzoyl peroxide.
Inorganic acid described in manufacturing method of the present invention is one of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, manufacturer of the present invention
Inorganic acid preferably sulfuric acid described in method, the reason is as follows that: 1. compared with nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid property is stablized, will not be light-exposed
It decomposes, it is not volatile, it will not deliquesce, have no irritating odor, more conducively industrial implementation；2. compared with nitric acid, hydrochloric acid, phosphoric acid, this
It is short that polymer solution made from inventing is frozen into the time used in fibre in sulfuric acid coagulating bath, and fibre forming property is best, receives filament and is
It is easy, therefore inorganic acid preferably sulfuric acid described in manufacturing method of the present invention.
Water soluble alkali described in manufacturing method of the present invention is sodium hydroxide, in lithium hydroxide, potassium hydroxide, barium hydroxide
One kind, the preferred sodium hydroxide of water soluble alkali described in manufacturing method of the present invention, the reason is as follows that: 1. with lithium hydroxide, potassium hydroxide
It compares, sodium hydroxide is cheap, is easy to get, more conducively industrial implementation；2. poly- in solvent preparation, dissolution compared with barium hydroxide
During closing object and swollen fiber, though sodium hydroxide and the carbon dioxide reaction in air, product be it is water-soluble, no
Easily remain on fiber, and barium hydroxide and Carbon Dioxide in Air reaction product are not soluble in water, easily remain on fiber,
Its subsequent applications is impacted；Based on above-mentioned two aspects reason, the preferred hydrogen-oxygen of water soluble alkali described in manufacturing method of the present invention
Change sodium.
Soluble ferrite described in manufacturing method of the present invention be one of frerrous chloride, ferrous sulfate, ferrous nitrate,
The preferred frerrous chloride of soluble ferrite described in manufacturing method of the present invention, the reason is as follows that: with ferrous sulfate, ferrous nitrate phase
Than frerrous chloride water solubility is more preferable, more stable, more conducively industrial implementation, for these reasons, described in manufacturing method of the present invention
The preferred frerrous chloride of soluble ferrite.
Specific embodiment is given below, the present invention to be described in further detail, but the claim of this application protection scope is not
It is limited by specific embodiment.
Embodiment 1
Two parts of acrylic acid are weighed, quality is respectively 11.6667g and 33.3333g, it places it in suitable beaker a, b,
5g hydroxyethyl methacrylate is weighed, hydroxyethyl methacrylate is poured into above-mentioned beaker a, 0.0833g benzoyl peroxide is weighed
Formyl adds it in above-mentioned beaker a, and stirring is dissolved completely in monomer up to benzoyl peroxide, weighs again
0.1667g benzoyl peroxide, and be added in beaker b, stirring is dissolved completely in monomer up to initiator, is weighed 50g and is gone
Ionized water is slowly added into above-mentioned beaker a, and stirring is uniformly mixed the liquid in beaker a, then turns mixed system
It moves in polymeric kettle, is passed through nitrogen to empty remaining air in polymeric kettle, opens stirring, open polymeric kettle heating system, to
When fluid temperature is increased to 85 DEG C in polymeric kettle, the solution in beaker b is added drop-wise in polymeric kettle dropwise, time for adding control exists
Within 30min, after completion of dropwise addition, after the reaction was continued 2h, gum-like product is taken out, is washed with deionized 5 times, removed unreacted
Monomer and oligomer are fully ground in high speed disintegrator after dry 96h under the conditions of 80 DEG C in vacuum drier, are made
Polymer powder, and seal spare；38.8g deionized water is weighed, is placed it in suitable beaker, 1.2g hydroxide is weighed
Sodium adds it in the above-mentioned beaker containing deionized water, and solvent is made after sodium hydroxide is completely dissolved；It is above-mentioned to weigh 2g
The polymer powder of synthesis adds a polymer in the above-mentioned beaker containing solvent, and magnetic agitation is carried out at 80 DEG C, to poly-
After conjunction object is dissolved completely in solvent, stops stirring and be simultaneously cooled to room temperature, spinning solution is made；80ml deionized water is measured, by it
It is placed in coagulating bath, measures the 20ml concentrated sulfuric acid, it is slowly poured into above-mentioned coagulating bath, stirring makes deionized water and the concentrated sulfuric acid
It is uniformly mixed, setting medium is made in cooled to room temperature；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, is utilized
Peristaltic pump drives above-mentioned spinning solution into polytetrafluoroethylene (PTFE) spinning pack with the speed of 0.6ml/min, to form dynamic analysis of spinning,
It is frozen into silk in 20 DEG C of coagulating baths, sufficiently after drying, can be obtained the fiber for being attached with inorganic acid salt；Repeatedly with deionized water
Washing is attached with the fiber of inorganic acid salt, and when the deionized water pH value of washed fiber is close to 7, washed fiber is immersed in
In the deionized water of certain mass, the mass ratio of fiber and deionized water is 0.01: 100, fills fiber in deionized water
Divide swelling, washing swelling time is 30min；The fiber being swollen is put into freeze-drying pallet, and this pallet is placed in very
In vacuum freecing-dry equipment cold-trap, it is freezed, fiber contained humidity is made all to condense into solid-state, condenser temperature is -80
DEG C, the fiber freezed is for 24 hours, is sent into vacuum freeze drying box by cooling time, until fiber sufficiently parches,
In the process, vacuum freeze drying room vacuum degree is 0Pa, drying time 20h, and being made has loose and porous structure fiber；
7.3765g deionized water is weighed, is placed it in suitable beaker, then weighs 2.2070g frerrous chloride tetrahydrate, is added into
Into above-mentioned deionized water, stirring is completely dissolved to it, weighs 0.0050g with loose and porous structure fiber, and fiber is soaked
Not in ferrous chloride aqueous solution, fiber is complexed with iron ion at 20 DEG C, after 240min, immediately by fiber from chlorine
Change and taken out in ferrous aqueous solution, be placed in high temperature furnace and carry out heat cross-linking, high temperature furnace temperature is 200 DEG C, and crosslinking time is
30min, atmosphere is air in high temperature furnace, then takes out fiber from high temperature furnace, is cooled to room temperature in the natural environment, is made
Fibrous heterogeneous Fenton catalyst.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 2min methylene blue is up to 97%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, and the removal rate of 3min methylene blue reaches
95%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in vacuum drying
In machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, and is led to
Enter 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution,
The removal rate of 40min methylene blue dye is up to 95%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the methylene of 20mg/L
Base indigo plant aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue dye is up to 37%；
Embodiment 2
The present embodiment technical process and parameter are same as Example 1, and only the heat cross-linking time is become by the 30min in embodiment 1
For 15min.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 2min methylene blue is up to 96%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, and the removal rate of 5min methylene blue reaches
95%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in vacuum drying
In machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, and is led to
Enter 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution,
The removal rate of 90min methylene blue dye is up to 72%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the methylene of 20mg/L
Base indigo plant aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue dye is up to 18%；
Embodiment 3
The present embodiment technical process and parameter are same as Example 1, and only the heat cross-linking time is become by the 30min in embodiment 1
For 25min.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 2min methylene blue is up to 97%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, the removal rate of 10min methylene blue
Up to 96%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is dry to be placed in vacuum
In dry machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added,
It is passed through 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution
In, the removal rate of 60min methylene blue dye is up to 95%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from Asia
It takes out, is placed in vacuum drier in methyl blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is 20mg/L's
Aqueous solution of methylene blue is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue dye is up to 30%.
Embodiment 4
The present embodiment technical process and parameter are same as Example 1, and only the heat cross-linking time is become by the 30min in embodiment 1
For 45min.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 2min methylene blue is up to 97%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, and the removal rate of 4min methylene blue reaches
95%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in vacuum drying
In machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, and is led to
Enter 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution,
The removal rate of 90min methylene blue dye is up to 92%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the methylene of 20mg/L
Base indigo plant aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue dye is up to 23%.
Embodiment 5
The present embodiment technical process and parameter are same as Example 1, and only the heat cross-linking time is become by the 30min in embodiment 1
For 60min.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 2min methylene blue is up to 95%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, and the removal rate of 5min methylene blue reaches
95%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in vacuum drying
In machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, and is led to
Enter 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution,
The removal rate of 90min methylene blue dye is up to 64%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the methylene of 20mg/L
Base indigo plant aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue dye is up to 19%.
Embodiment 6
The present embodiment technical process and parameter are same as Example 1, and only heat cross-linking temperature is by 200 DEG C of changes in embodiment 1
It is 100 DEG C.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 2min methylene blue is up to 96%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, the removal rate of 90min methylene blue
Up to 91%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is dry to be placed in vacuum
In dry machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added,
It is passed through 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution
In, the removal rate of 90min methylene blue dye is up to 22%.
Embodiment 7
The present embodiment technical process and parameter are same as Example 1, and only heat cross-linking temperature is by 200 DEG C of changes in embodiment 1
It is 150 DEG C.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 2min methylene blue is up to 96%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, the removal rate of 60min methylene blue
Up to 95%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is dry to be placed in vacuum
In dry machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added,
It is passed through 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution
In, the removal rate of 90min methylene blue dye is up to 22%.
Embodiment 8
The present embodiment technical process and parameter are same as Example 1, and only heat cross-linking temperature is by 200 DEG C of changes in embodiment 1
It is 250 DEG C.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 40min methylene blue is up to 95%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from Asia
It takes out, is placed in vacuum drier in methyl blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is 20mg/L's
Aqueous solution of methylene blue is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue is up to 22%.
Embodiment 9
The present embodiment technical process and parameter are same as Example 1, and only heat cross-linking temperature is by 200 DEG C of changes in embodiment 1
It is 300 DEG C.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 2min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 15min methylene blue
Removal rate is up to 96%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in
In vacuum drier, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l are added
Hydrogen peroxide is passed through 1min ozone, will complete second of catalysis and dry fibrous heterogeneous Fenton catalyst is placed in
It states in solution, the removal rate of 90min methylene blue is up to 26%.Embodiment 10
The present embodiment technical process and parameter are same as Example 1, and only the ferrous ion time is complexed by embodiment 1 in fiber
240min become 60min, the heat cross-linking time becomes 15min from the 30min in embodiment 1.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 15min methylene blue is up to 96%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, the removal rate of 90min methylene blue
Up to 72%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is dry to be placed in vacuum
In dry machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added,
It is passed through 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution
In, the removal rate of 90min methylene blue is up to 22%.
Embodiment 11
Two parts of acrylic acid are weighed, quality is respectively 23.3333g and 16.6667g, it places it in suitable beaker a, b,
10g hydroxyethyl methacrylate is weighed, hydroxyethyl methacrylate is poured into above-mentioned beaker a, 0.1667g benzoyl peroxide is weighed
Formyl adds it in above-mentioned beaker a, and stirring is dissolved completely in monomer up to benzoyl peroxide, weighs again
0.0833g benzoyl peroxide, and be added in beaker b, stirring is dissolved completely in monomer up to initiator, is weighed 50g and is gone
Ionized water is slowly added into above-mentioned beaker a, and stirring is uniformly mixed the liquid in beaker a, then turns mixed system
It moves in polymeric kettle, is passed through nitrogen to empty remaining air in polymeric kettle, opens stirring, open polymeric kettle heating system, to
When fluid temperature is increased to 85 DEG C in polymeric kettle, the solution in beaker b is added drop-wise in polymeric kettle dropwise, time for adding control exists
Within 30min, after completion of dropwise addition, after the reaction was continued 2h, gum-like product is taken out, is washed with deionized 5 times, removed unreacted
Monomer and oligomer are fully ground in high speed disintegrator after dry 96h under the conditions of 80 DEG C in vacuum drier, are made
Polymer powder, and seal spare；38g deionized water is weighed, is placed it in suitable beaker, 2g sodium hydroxide is weighed,
It adds it in the above-mentioned beaker containing deionized water, solvent is made after sodium hydroxide is completely dissolved；Weigh the above-mentioned conjunction of 2g
At polymer powder, add a polymer in the above-mentioned beaker containing solvent, magnetic agitation carried out at 80 DEG C, it is to be polymerized
After object is dissolved completely in solvent, stops stirring and being cooled to room temperature, spinning solution is made；80ml deionized water is measured, is set
In coagulating bath, the 20ml concentrated sulfuric acid is measured, it is slowly poured into above-mentioned coagulating bath, stirring keeps deionized water and the concentrated sulfuric acid mixed
It closes uniformly, setting medium is made in cooled to room temperature；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, utilization is compacted
Dynamic pump drives above-mentioned spinning solution into polytetrafluoroethylene (PTFE) spinning pack with the speed of 0.6ml/min, to form dynamic analysis of spinning, In
It is frozen into silk in 20 DEG C of coagulating baths, sufficiently after drying, can be obtained the fiber for being attached with inorganic acid salt；It is washed repeatedly with deionized water
The fiber for being attached with inorganic acid salt is washed, when the deionized water pH value of washed fiber is close to 7, washed fiber is immersed in one
Determine in the deionized water of quality, the mass ratio of fiber and deionized water is 0.01: 100, keeps fiber abundant in deionized water
Swelling, washing swelling time are 30min；The fiber being swollen is put into freeze-drying pallet, and this pallet is placed in vacuum
In freeze drying equipment cold-trap, it is freezed, fiber contained humidity is made all to condense into solid-state, condenser temperature is -80 DEG C,
The fiber freezed is for 24 hours, is sent into vacuum freeze drying box by cooling time, until fiber sufficiently parches, In
During this, vacuum freeze drying room vacuum degree is 0Pa, drying time 20h, and being made has loose and porous structure fiber；Claim
7.3765g deionized water is taken, is placed it in suitable beaker, then weighs 2.2070g frerrous chloride tetrahydrate, is added it to
In above-mentioned deionized water, stirring is completely dissolved to it, weighs 0.0050g with loose and porous structure fiber, and fiber is submerged
In ferrous chloride aqueous solution, fiber is complexed with iron ion at 20 DEG C, after 60min, immediately by fiber from chlorination
It being taken out in ferrous aqueous solution, is placed in high temperature furnace and carries out heat cross-linking, high temperature furnace temperature is 200 DEG C, crosslinking time 15min,
Atmosphere is air in high temperature furnace, then takes out fiber from high temperature furnace, is cooled to room temperature in the natural environment, and threadiness is made
Heterogeneous Fenton catalyst.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mgL, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be fibrous
Heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fibrous
Heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, under the conditions of 40 DEG C
Dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, is passed through 1min ozone, will complete
It is catalyzed for the first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, the removal of 1min methylene blue
Rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in vacuum
In drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l dioxygens are added
Water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned molten
In liquid, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the methylene of 20mgL
Base indigo plant aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 60min methylene blue is up to 95%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, the removal rate of 90min methylene blue
Up to 22%.
Embodiment 12
A acrylic acid is weighed, quality 35g is placed it in suitable beaker a, weighs 15g hydroxyethyl methacrylate second
Hydroxyethyl methacrylate is poured into above-mentioned beaker a, weighs 0.25g benzoyl peroxide, adds it to above-mentioned beaker by ester
In a, stirring is dissolved completely in monomer up to benzoyl peroxide, is weighed 50g deionized water, is slowly added into above-mentioned burning
In cup a, stirring is uniformly mixed the liquid in beaker a, and then mixed system is transferred in polymeric kettle, is passed through nitrogen to empty
Remaining air in polymeric kettle opens stirring, opens polymeric kettle heating system, and fluid temperature is increased to 85 DEG C in kettle to be polymerized
When, start timing, after reacting 2.5h, takes out gum-like product, be washed with deionized 5 times, remove unreacted monomer and low
Polymers is fully ground in high speed disintegrator after dry 96h under the conditions of 80 DEG C in vacuum drier, powdered polymeric is made
Object, and seal spare；32g deionized water is weighed, is placed it in suitable beaker, 8g sodium hydroxide is weighed, adds it to
In the above-mentioned beaker containing deionized water, solvent is made after sodium hydroxide is completely dissolved；Weigh the polymer of the above-mentioned synthesis of 2g
Powder adds a polymer in the above-mentioned beaker containing solvent, and magnetic agitation is carried out at 80 DEG C, and object to be polymerized is completely dissolved
After solvent, stops stirring and being cooled to room temperature, spinning solution is made；80ml deionized water is measured, is placed it in coagulating bath,
The 20ml concentrated sulfuric acid is measured, it is slowly poured into above-mentioned coagulating bath, stirring is uniformly mixed deionized water and the concentrated sulfuric acid, natural
It is cooled to room temperature obtained setting medium；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, it will be above-mentioned using peristaltic pump
Spinning solution is driven with the speed of 0.6ml/min into polytetrafluoroethylene (PTFE) spinning pack, to form dynamic analysis of spinning, in 20 DEG C of coagulating baths
In be frozen into silk, after sufficiently dry, can be obtained the fiber for being attached with inorganic acid salt；It is washed repeatedly with deionized water and is attached with nothing
Washed fiber is immersed in going for certain mass when the deionized water pH value of washed fiber is close to 7 by the fiber of machine hydrochlorate
In ionized water, the mass ratio of fiber and deionized water is 0.01: 100, is swollen fiber sufficiently in deionized water, is washed molten
The swollen time is 30min；The fiber being swollen is put into freeze-drying pallet, and this pallet is placed in vacuum freeze
In cold-trap, it is freezed, fiber contained humidity is made all to condense into solid-state, condenser temperature is -80 DEG C, and cooling time is
For 24 hours, the fiber freezed is sent into vacuum freeze drying box, until fiber sufficiently parches, in the process, very
Vacuum freecing-dry room vacuum degree is 0Pa, drying time 20h, and being made has loose and porous structure fiber；7.3765g is weighed to go
Ionized water places it in suitable beaker, then weighs 2.2070g frerrous chloride tetrahydrate, adds it to above-mentioned deionization
In water, stirring is completely dissolved to it, weighs 0.0050g with loose and porous structure fiber, and fiber is immersed in frerrous chloride
In aqueous solution, fiber is complexed with iron ion at 20 DEG C, after 60min, immediately by fiber from ferrous chloride aqueous solution
Middle taking-up is placed in high temperature furnace and carries out heat cross-linking, and high temperature furnace temperature is 200 DEG C, crosslinking time 15min, gas in high temperature furnace
Atmosphere is air, then takes out fiber from high temperature furnace, is cooled to room temperature in the natural environment, and threadiness heterophase Fenton is made
Catalysts.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 2min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 40min methylene blue is up to 95%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from Asia
It takes out, is placed in vacuum drier in methyl blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is 20mg/L's
Aqueous solution of methylene blue is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue is up to 23%.
Embodiment 13
A acrylic acid is weighed, quality 30g is placed it in suitable beaker a, weighs 20g hydroxyethyl methacrylate second
Hydroxyethyl methacrylate is poured into above-mentioned beaker a, weighs 0.25g benzoyl peroxide, adds it to above-mentioned beaker by ester
In a, stirring is dissolved completely in monomer up to benzoyl peroxide, is weighed 50g deionized water, is slowly added into above-mentioned burning
In cup a, stirring is uniformly mixed the liquid in beaker a, and then mixed system is transferred in polymeric kettle, is passed through nitrogen to empty
Remaining air in polymeric kettle opens stirring, opens polymeric kettle heating system, and fluid temperature is increased to 85 DEG C in kettle to be polymerized
When, start timing, after reacting 2.5h, takes out gum-like product, be washed with deionized 5 times, remove unreacted monomer and low
Polymers is fully ground in high speed disintegrator after dry 96h under the conditions of 80 DEG C in vacuum drier, powdered polymeric is made
Object, and seal spare；32g deionized water is weighed, is placed it in suitable beaker, 8g sodium hydroxide is weighed, adds it to
In the above-mentioned beaker containing deionized water, solvent is made after sodium hydroxide is completely dissolved；Weigh the polymer of the above-mentioned synthesis of 2g
Powder adds a polymer in the above-mentioned beaker containing solvent, and magnetic agitation is carried out at 80 DEG C, and object to be polymerized is completely dissolved
After solvent, stops stirring and being cooled to room temperature, spinning solution is made；80ml deionized water is measured, is placed it in coagulating bath,
The 20ml concentrated sulfuric acid is measured, it is slowly poured into above-mentioned coagulating bath, stirring is uniformly mixed deionized water and the concentrated sulfuric acid, natural
It is cooled to room temperature obtained setting medium；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, it will be above-mentioned using peristaltic pump
Spinning solution is driven with the speed of 0.6ml/min into polytetrafluoroethylene (PTFE) spinning pack, to form dynamic analysis of spinning, in 20 DEG C of coagulating baths
In be frozen into silk, after sufficiently dry, can be obtained the fiber for being attached with inorganic acid salt；It is washed repeatedly with deionized water and is attached with nothing
Washed fiber is immersed in going for certain mass when the deionized water pH value of washed fiber is close to 7 by the fiber of machine hydrochlorate
In ionized water, the mass ratio of fiber and deionized water is 0.01: 100, is swollen fiber sufficiently in deionized water, is washed molten
The swollen time is 30min；The fiber being swollen is put into freeze-drying pallet, and this pallet is placed in vacuum freeze
In cold-trap, it is freezed, fiber contained humidity is made all to condense into solid-state, condenser temperature is -80 DEG C, and cooling time is
For 24 hours, the fiber freezed is sent into vacuum freeze drying box, until fiber sufficiently parches, in the process, very
Vacuum freecing-dry room vacuum degree is 0Pa, drying time 20h, and being made has loose and porous structure fiber；7.3765g is weighed to go
Ionized water places it in suitable beaker, then weighs 2.2070g frerrous chloride tetrahydrate, adds it to above-mentioned deionization
In water, stirring is completely dissolved to it, weighs 0.0050g with loose and porous structure fiber, and fiber is immersed in frerrous chloride
In aqueous solution, fiber is complexed with iron ion at 20 DEG C, after 60min, immediately by fiber from ferrous chloride aqueous solution
Middle taking-up is placed in high temperature furnace and carries out heat cross-linking, and high temperature furnace temperature is 200 DEG C, crosslinking time 15min, gas in high temperature furnace
Atmosphere is air, then takes out fiber from high temperature furnace, is cooled to room temperature in the natural environment, and threadiness heterophase Fenton is made
Catalysts.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 5min methylene blue is gone
Except rate is up to 95%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 90min methylene blue is up to 85%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from Asia
It takes out, is placed in vacuum drier in methyl blue aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is 20mg/L's
Aqueous solution of methylene blue is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue is up to 22%.
Embodiment 14
Two parts of acrylic acid are weighed, quality is respectively 11.6667g and 33.3333g, it places it in suitable beaker a, b,
5g hydroxyethyl methacrylate is weighed, hydroxyethyl methacrylate is poured into above-mentioned beaker a, 0.0833g benzoyl peroxide is weighed
Formyl adds it in above-mentioned beaker a, and stirring is dissolved completely in monomer up to benzoyl peroxide, weighs again
0.1667g benzoyl peroxide, and be added in beaker b, stirring is dissolved completely in monomer up to initiator, is weighed 50g and is gone
Ionized water is slowly added into above-mentioned beaker a, and stirring is uniformly mixed the liquid in beaker a, then turns mixed system
It moves in polymeric kettle, is passed through nitrogen to empty remaining air in polymeric kettle, opens stirring, open polymeric kettle heating system, to
When fluid temperature is increased to 85 DEG C in polymeric kettle, the solution in beaker b is added drop-wise in polymeric kettle dropwise, time for adding control exists
Within 30min, after completion of dropwise addition, after the reaction was continued 2h, gum-like product is taken out, is washed with deionized 5 times, removed unreacted
Monomer and oligomer are fully ground in high speed disintegrator after dry 96h under the conditions of 80 DEG C in vacuum drier, are made
Polymer powder, and seal spare；38.8g deionized water is weighed, is placed it in suitable beaker, 1.2g hydroxide is weighed
Sodium adds it in the above-mentioned beaker containing deionized water, and solvent is made after sodium hydroxide is completely dissolved；It is above-mentioned to weigh 2g
The polymer powder of synthesis adds a polymer in the above-mentioned beaker containing solvent, and magnetic agitation is carried out at 80 DEG C, to poly-
After conjunction object is dissolved completely in solvent, stops stirring and be simultaneously cooled to room temperature, spinning solution is made；80ml deionized water is measured, by it
It is placed in coagulating bath, measures the 20ml concentrated sulfuric acid, it is slowly poured into above-mentioned coagulating bath, stirring makes deionized water and the concentrated sulfuric acid
It is uniformly mixed, setting medium is made in cooled to room temperature；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, is utilized
Peristaltic pump drives above-mentioned spinning solution into polytetrafluoroethylene (PTFE) spinning pack with the speed of 0.6ml/min, to form dynamic analysis of spinning,
It is frozen into silk in 20 DEG C of coagulating baths, sufficiently after drying, can be obtained the fiber for being attached with inorganic acid salt；Repeatedly with deionized water
Washing is attached with the fiber of inorganic acid salt, when the deionized water pH value of washed fiber is close to 7, by washed fiber be placed in from
It is dry under right environment to weigh 9.990g deionized water for 24 hours, place it in suitable beaker, then weigh 0.0100g sodium hydroxide,
It adding it in above-mentioned deionized water, stirring is completely dissolved to sodium hydroxide, the fiber of 0.0050g natural air drying is weighed, and
Fiber is immersed in sodium hydrate aqueous solution, is swollen fiber at 20 DEG C, after 60min is swollen, repeatedly with deionized water
Fiber is washed, until the deionized water pH value of washed fiber is close to 7, being made has loose and porous structure fiber；It weighs
7.3765g deionized water places it in suitable beaker, then weighs 2.2070g frerrous chloride tetrahydrate, adds it to
It states in deionized water, stirs to it and be completely dissolved, and loose and porous structure fiber is immersed in ferrous chloride aqueous solution, 20
Fiber is complexed with iron ion at DEG C, after 60min, fiber is taken out from ferrous chloride aqueous solution immediately, is placed in
Heat cross-linking is carried out in high temperature furnace, high temperature furnace temperature is 200 DEG C, crosslinking time 30min, and atmosphere is air in high temperature furnace, then
Fiber is taken out from high temperature furnace, is cooled to room temperature in the natural environment, threadiness heterogeneous Fenton catalyst is made.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 1min methylene blue is up to 97%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 3min methylene blue is up to 97%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, the removal rate of 90min methylene blue
Up to 88%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is dry to be placed in vacuum
In dry machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added,
It is passed through 1min ozone, the 5th catalysis will be completed and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution
In, the removal rate of 90min methylene blue dye is up to 18%.
Embodiment 15
The present embodiment technical process and parameter are identical as embodiment 14, and only heat cross-linking temperature is by 200 DEG C of changes in embodiment 1
It is 300 DEG C.
Taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, 1min ozone are passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the removal rate of 1min methylene indigo plant is 97%；At this point, by fiber
Shape heterogeneous Fenton catalyst takes out from aqueous solution of methylene blue rapidly, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will be complete
It is catalyzed at first time and dry fibrous heterogeneous Fenton catalyst is placed in above-mentioned solution, 1min methylene blue is gone
Except rate is up to 97%；At this point, fibrous heterogeneous Fenton catalyst is taken out from aqueous solution of methylene blue rapidly, it is placed in true
In empty drying machine, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and it is bis- that 2 μ l are added
Oxygen water is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will complete to be catalyzed and dry for the second time is placed in above-mentioned
In solution, the removal rate of 4min methylene blue is up to 96%；At this point, by fibrous heterogeneous Fenton catalyst rapidly from methylene
It takes out, is placed in vacuum drier in base indigo plant aqueous solution, dry 1.5h under the conditions of 40 DEG C, taking 10ml concentration is the Asia of 20mg/L
Methyl blue aqueous solution is added 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete third time catalysis and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the removal rate of 90min methylene blue is up to 82%；At this point, by fibrous out-phase
Fenton catalysts take out from aqueous solution of methylene blue rapidly, are placed in vacuum drier, dry under the conditions of 40 DEG C
1.5h, taking 10ml concentration is the aqueous solution of methylene blue of 20mg/L, and 2 μ l hydrogen peroxide are added, are passed through 1min ozone, will complete the 4th
The fibrous heterogeneous Fenton catalyst of secondary catalysis and drying is placed in above-mentioned solution, the removal rate of 90min methylene blue
Up to 19%.
Claims (6)
1. a kind of manufacturing method of threadiness heterogeneous Fenton catalyst, it is characterised in that technical process is as follows:
(1) Precipitation Polymerization Process: weighing two parts of monomers 1, is placed it in suitable beaker a, b respectively, makes the monomer in beaker a
1 mass ratio of monomer in 1 and beaker b is 10: 0~0: 10, does not include two endpoints, weighs the monomer 2 of certain mass, make list
The ratio between gross mass of body 2 and two parts of monomers 1 is 0: 10~4: 6, does not include 0: 10, and monomer 2 is poured into above-mentioned beaker a, is claimed
The initiator for taking certain mass makes 0.2~2% of 2 gross mass of monomer 1 and monomer in initiator quality beaker a, and is added
Enter into above-mentioned beaker a, stirring is dissolved completely in monomer up to initiator, is weighed initiator again, is made initiator quality
The 0.2~2% of 1 mass of monomer in above-mentioned beaker b, and it is added to above-mentioned beaker b, stirring is until initiator is dissolved completely in monomer
In, appropriate amount of deionized water is weighed, making the ratio between itself and 2 gross mass of monomer 1 and monomer is 1: 2~2: 1, and is slowly added into
State in beaker a, stirring is uniformly mixed liquid in beaker a, and then mixed system is transferred in polymeric kettle, be passed through nitrogen with
Remaining air in polymeric kettle is emptied, stirring is opened, opens polymeric kettle heating system, fluid temperature is increased to 70 in kettle to be polymerized
At~95 DEG C, the monomer 1 in beaker b containing initiator is added drop-wise in polymeric kettle dropwise, time for adding control 10~60min it
Interior, after completion of dropwise addition, the reaction was continued 1~4h takes out gum-like product, is washed with deionized more than once, removes unreacted
Monomer and oligomer are sufficiently ground in high speed disintegrator after dry 48~96h under the conditions of 40~80 DEG C in vacuum drier
Polymer powder is made in mill, and seals spare, and the monomer 1 is acrylic acid, methacrylic acid, in maleic anhydride
One kind, and the monomer 2 is one of hydroxyethyl methacrylate, hydroxy propyl methacrylate；
(2) wet spinning technology: weighing certain mass deionized water, places it in suitable beaker, and weighing certain mass can
Dissolubility alkali makes the mass ratio 0.0001: 9.9999~9.5000: 0.5000 of water soluble alkali and deionized water, is added into
Into the above-mentioned beaker containing deionized water, solvent is made after water soluble alkali is completely dissolved；It weighs in certain mass step (1)
Polymer powder obtained makes the mass ratio 0.1: 10~3: 10 of polymer Yu above-mentioned solvent, adds a polymer to
It states in the beaker containing solvent, magnetic agitation is carried out at 40~80 DEG C, after object to be polymerized is dissolved completely in solvent, stop stirring
It mixes and is cooled to room temperature, spinning solution is made；The deionized water for measuring certain volume, places it in coagulating bath, measures certain
The inorganic acid of volume, making the ratio between volume of inorganic acid and deionized water is 0.2: 9.8~9.8: 0.2, it is slowly poured into
It states in coagulating bath, stirring is uniformly mixed deionized water and inorganic acid, and setting medium is made in cooled to room temperature；By polytetrafluoro
Ethylene spinning pack is immersed in setting medium, is driven above-mentioned spinning solution to polytetrafluoroethylene (PTFE) spinning pack using peristaltic pump
In, to form dynamic analysis of spinning, dynamic analysis of spinning is frozen into silk in coagulating bath, sufficiently after drying, can be obtained and is attached with inorganic acid
The fiber of salt；
(3) specially treated technique: A technique is attached to fiber obtained in deionized water repeatedly washing step (2) with removing
Washed fiber is immersed in certain matter when the deionized water pH value of washed fiber is close to 7 by the inorganic acid salt of fiber surface
It in the deionized water of amount, is swollen fiber sufficiently in deionized water, above-mentioned swollen fiber is placed in vacuum freeze
In freezed, dried, condenser temperature is -80 DEG C~-40 DEG C, and cooling time is 12~36h, and vacuum degree is 0Pa~100Pa,
Drying time is 12~36h, is sufficiently parched to fiber, and being made has loose and porous structure fiber；B technique, it is anti-with deionized water
Fiber obtained in multiple washing step (2), to remove the inorganic acid salt for being attached to fiber surface, when the deionization of washed fiber
When water pH value is close to 7, washed fiber is placed under natural environment dry 24~96h, weighs the deionized water of certain mass, it will
It is placed in suitable beaker, then weighs a certain amount of water soluble alkali, and water soluble alkali is added in above-mentioned deionized water, and stirring is extremely
Water soluble alkali is completely dissolved, and the water soluble alkali aqueous solution that mass percent concentration is 0.01%~3% is made, by natural air drying
Fiber is immersed in water soluble alkali aqueous solution, so that fiber is sufficiently swollen, then washs fiber repeatedly with deionized water, until washing
The deionized water pH value of fiber was washed close to 7, being made has loose and porous structure fiber；
(4) complexing technique: weighing certain mass deionized water, places it in suitable beaker, then weighs and deionized water quality
Than the soluble ferrite for 0: 10~10: 0, do not include two endpoints, add it in above-mentioned deionized water, stirring extremely may be used
Dissolubility ferrous salt is completely dissolved；Take fiber obtained in step (3), make fiber and above-mentioned soluble ferrite aqueous solution quality it
Do not include 0: 10 than being 0: 10~10: 10, and fiber is immersed in soluble ferrite aqueous solution, makes at 20~80 DEG C
Fiber is complexed with iron ion, after several seconds~300min is complexed, is immediately taken out fiber from perferrite solution, is obtained network
Close the fiber for having ferrous ion；
(5) heat cross-linking technique: the fiber that the complexing that step (4) obtain has ferrous ion being placed in high temperature furnace and carries out heat cross-linking,
High temperature furnace temperature is 100~300 DEG C, and crosslinking time is 5~80min, in high temperature furnace atmosphere can for air, nitrogen or helium,
Fiber is then taken out from high temperature furnace, is cooled to room temperature in the natural environment by neon, argon gas, Krypton, xenon, and fiber is made
Shape heterogeneous Fenton catalyst.
2. a kind of manufacturing method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
The initiator is benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, peroxidating
One of diisopropylbenzene (DIPB), di-t-butyl peroxide.
3. a kind of manufacturing method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
The inorganic acid is one of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid.
4. a kind of manufacturing method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
The water soluble alkali is one of sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide.
5. a kind of manufacturing method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
The soluble ferrite is one of frerrous chloride, ferrous sulfate, ferrous nitrate.
6. a kind of manufacturing method of fibrous heterogeneous Fenton catalyst according to any one of claims 1 to 5,
It is characterized in that the monomer 1 is acrylic acid, the monomer 2 is hydroxyethyl methacrylate, and the initiator was
Benzoyl Oxide, the inorganic acid are sulfuric acid, and the water soluble alkali is sodium hydroxide, and the soluble ferrite is chlorine
Change ferrous.
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