CN107308938A - A kind of manufacture method of fibrous heterogeneous Fenton catalyst - Google Patents
A kind of manufacture method of fibrous heterogeneous Fenton catalyst Download PDFInfo
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- CN107308938A CN107308938A CN201710530870.3A CN201710530870A CN107308938A CN 107308938 A CN107308938 A CN 107308938A CN 201710530870 A CN201710530870 A CN 201710530870A CN 107308938 A CN107308938 A CN 107308938A
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- fiber
- deionized water
- aqueous solution
- monomer
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- 238000000034 method Methods 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
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- 238000001035 drying Methods 0.000 claims description 56
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- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000002341 toxic gas 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
Classifications
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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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Engineering & Computer Science (AREA)
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- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the design of functional fibre material in textile material field and manufacture, be related to a kind of preparation of fibrous heterogeneous Fenton catalyst, specially one kind can catalytic oxidant (such as hydrogen peroxide, ozone) is quick, efficient oxidation decomposes a variety of dyestuffs, it is reusable, be easy to the manufacture method of fiber that is separated with water body.The technologies such as the manufacture method integrated use precipitation polymerization, wet spinning, penetrating power lifting, iron ion complexing, heat cross-linking, gained fiber 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 Fenton catalysts made from same type wet spinning process fiber, the Speed Efficient oxidation Decomposition organic matter that can be exceedingly fast, quick, effective purification to water body is realized, while reusability is significantly improved, application cost reduction, therefore, industrial applicibility requirement is more met.
Description
Technical field
The invention belongs to the design of functional fibre material in textile material field and manufacture, it is related to a kind of fibrous out-phase
The preparation of Fenton catalysts, specially one kind can catalytic oxidant (such as hydrogen peroxide, ozone) be quick, efficient oxidation
Decompose a variety of dyestuffs, it is reusable, be easy to the manufacture method of fiber that is separated with water body.The manufacture method integrated use is heavy
The technologies such as shallow lake polymerization, wet spinning, penetrating power lifting, iron ion complexing, heat cross-linking, gained fiber can be used for waste water from dyestuff etc.
The processing of the water body containing organic matter.
Background technology
With the fast development and the continuous progress of industry of society, the existence of the water pollution problems being on the rise to the mankind
Safety constitutes significant threat, the major obstacles as human health, economy and social sustainable development.And textile printing and dyeing industry is made
For typical highly water intensive industry, production process process is sufficiently complex, and nearly hundred million tons of water need to be consumed every year, substantial amounts of dyestuff is thus produced
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 into
It is point sufficiently complex, with the features such as water is big, change of water quality is big, content of organics is high, colourity is high, biodegradability is poor, and contain more
Organic matter with bio-toxicity or " three cause property " (carcinogenic, teratogenesis and mutagenicity), directly discharge can be brought to living environment
High risks, while the waste of water resource is caused, and with country and the social pay attention to day by day to environmental protection requirement, it is traditional
Dye waste water treatment method can not meet production and environmental protection requirement, therefore, current dye wastewater treatment field in the 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 1980s, countries in the world environmental science and technology has been caused using the high-level oxidation technology for generating OH as mark
The attention on boundary, because high-level oxidation technology has oxidability strong and the features such as non-secondary pollution, so be considered as to handle water
Middle hardly degraded organic substance most has the technology of application prospect.Compared with other high-level oxidation technologies, Fenton methods are due to reaction
Rapidly, oxidability is strong, good decolorizing effect and the features such as strong flexibility, it is considered to be widely used and great development potentiality at present
One of dye waste water treatment method.Fenton systems pass through Fe2+With H2O2Reaction OH of the generation with high reaction activity,
, can be with oxidation Decomposition organic pollution and OH has the Strong oxdiative ability for being only second to fluorine, it is used as production in the middle of oxidizing process
Thing, can induce chain reaction below, the material of some difficult for biological degradation is transformed into the material of easy biological treatment, and
The color development or auxochrome group of dyestuff are destroyed, it is lost color development ability, so that coloring matter is degraded, organic pollution is thorough
It is harmless to turn to carbon dioxide and water.Chemical reaction condition needed for Fenton systems gently, is easily realized, and oxidation reaction does not have
Have other poisonous and harmful substances of introducing, be 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).
At present, Fenton reaction systems mainly include the homogeneous and big reaction system of out-phase two, are further raising organic matter
Removal effect, by optics, ultrasonic technology and electrochemical techniques etc. be dissolved into Fenton reaction in form novel homogeneous
Fenton reaction systems (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), it is but common homogeneous
Fenton reaction systems have the absolute predominance in terms of cost and technical feasibility, therefore are still that Fenton methods processing dyestuff gives up
The reaction system commonly used during water.But for common homogeneous Fenton reaction systems, because its only under relatively low pH
It can effectively carry out, it is necessary to adjust waste water repeatedly pH value to acidity, increasing processing cost, and homogeneous Fenton reaction systems
Catalyst it is miscible in waste water in the form of an ion, homogeneous catalyst and reactant, reaction product mixing, cause after use be catalyzed
Agent is difficult to separate, and produces a large amount of iron cements, and post processing is complicated, wastes reaction resource, and improves use cost, limits homogeneous
The application of Fenton reaction systems.
With in Fenton reaction systems catalyst research deeply and mankind's environmental consciousness enhancing, by divalence or
Ferric ion, other ions and compound ion are supported on certain carrier, form heterogeneous Fenton catalyst, different
Phase Fenton reaction systems can handle waste water from dyestuff in the range of wide pH, i.e., organic molecule is adsorbed onto into catalyst table first
Face, in active component and H2O2In the presence of, organic molecule is decomposed, and the product desorption after degraded is simultaneously returned in solution, and then
Pollutant process is completed, and heterogeneous Fenton catalyst can be separated with aqueous systems easily, and then can repeatedly use,
During this, because the iron ion amount of elution is few, therefore a large amount of iron cements (Zeng X, Lemley A T, Fenton will not be produced
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 systems had both remained the advantage of homogeneous Fenton reactions, and significantly compensate for its deficiency, were greatly simplifying processing
On process base, it can greatly expand wastewater treatment scope, it has also become Fenton methods handle an important development of organic wastewater
Direction, will also play a positive role in the treatment of waste water, with fabulous application prospect.
At present, 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 systems, and carrier can be had
Airborne body or inorganic carrier, Nafion membrane are a kind of cation exchanges being made up of perfluorinated sulfonic acid anionic polymer
Film, has the advantages that heat-resisting, corrosion-resistant and intensity is high, but because 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 can also 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 the oxide etch for being subjected to OH.In inorganic material, aluminum 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 is kaolin, frequently as iron ion carrier (Li Huanyu, it is heterogeneous
The progress of Fenton reaction treatment organic pollutions, building and budget, 2015,06：47-50), using inorganic material as carrier
Heterogeneous Fenton catalyst have cost low, specific surface area is high and the advantage such as high adsorption capacity, but catalyst preparation mistake
Journey is complicated, and fine catalyst is difficult to reclaim, and its 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 nonmagnetic substance has bloodstone and pin iron
Ore deposit etc., iron powder and these mineral materials itself just can be with H2O2Constitute Fenton systems 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 systems
Influenceed larger by pH, in acid condition, the dissolution of iron ion can induce H2O2OH is produced, but the iron ion of dissolution is eventually given birth to
Into iron cement, cause secondary pollution, and ore iron species is less and limited source, limit it and further apply.
Under above-mentioned background, novel carriers material is researched and developed, enables iron ion or iron oxide firmly and equal
It is supported on evenly thereon, solid-liquid is easily isolated 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, is synthesized using precipitation polymerization method rich in the poly- of specific functional groups carboxyl, hydroxyl etc.
The polymer of synthesis, is then dissolved in the water soluble alkali aqueous solution by compound, using this solution as spinning solution, with inorganic acid aqueous solution
For setting medium, using wet spinning technology spinning fibre, and handled through special process, loose and porous structure is assigned after shaping
Fiber, to reduce iron ion absorption, it is fixed when osmotic resistance so that make within the limited time fibrous inside be full of iron from
Son, iron ion load capacity increase, through thermal crosslinking treatment after, makes to be dehydrated between amount of activated group carboxyl and hydroxyl and formed and handed over
Join network structure, cross-linked network structure constraint iron ion, along with the strong complexing between carboxyl, hydroxyl and iron ion and
The constraint effect of fiber surface, makes iron ion more be securely joined with fibrous inside, iron ion washes when greatly reduction is applied
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 formation of iron species are carried out
Modification, further enhances its catalytic activity, is reaching for above-mentioned water body to the processing for water bodys containing organic matter such as waste water from dyestuff
The new processing material of mark discharge exploitation.
The content of the invention
In view of the shortcomings of the prior art, the technical problem that the present invention is intended to solve is to provide a kind of fibrous heterophase Fenton
The manufacture method of catalysts.The manufacture method selects suitable monomer first on the basis of prior art invention, using heavy
Polymer of the shallow lake polymerization synthesis rich in specific functional groups carboxyl, hydroxyl etc., then dissolves a polymer in the 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 fiber, in the soluble ferrite aqueous solution, because loose and porous structure draws by loose and porous structure
The hyposmosis resistance of hair, iron ion quickly enters fibrous inside by solution, and is complexed with carboxyl, hydroxyl, along with fiber surface
Constraint, iron ion is firmly fixed at fibrous inside, after thermal crosslinking treatment, between part carboxyl and hydroxyl dehydration and shape
Into cross-linked network structure, iron ion is set more to be securely joined with fibrous inside, iron ion is difficult to be eluted, and fiber is provided with different
Phase Fenton catalytic reaction functions.Gained fiber is compared with conventional Fenton catalysts, except with fiber consumption is few, H2O2
The organic removal rates such as consumption is low, pH is applied widely, dyestuff are high, remove outside the advantages of speed is fast, also with can be non-woven
Or textile process, it is easy to use, the advantages of can reclaim easily, more meet the requirement of industrial applicibility.
The technical scheme that the present invention solves the technical problem is：Design a kind of fibrous heterogeneous Fenton catalyst
Manufacture method, its technical process is as follows：
(1) Precipitation Polymerization Process：Two parts of monomers 1 are weighed, is placed in suitable beaker a, b, makes in beaker a respectively
The mass ratio of monomer 1 in monomer 1 and beaker b is 10: 0~0: 10, not including two end points, weighs the monomer 2 of certain mass,
It is 0: 10~4: 6 to make the ratio between gross mass of monomer 2 and two parts of monomers 1, not including 0: 10, and monomer 2 is poured into above-mentioned beaker a
In, the initiator of certain mass is weighed, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and
Add it in above-mentioned beaker a, stirring is dissolved completely in monomer up to initiator, and initiator is weighed again, makes initiator
Quality is 0.2~2% of the mass of monomer 1 in above-mentioned beaker b, and is added to above-mentioned beaker b, stirring until initiator is completely dissolved
In monomer, appropriate amount of deionized water is weighed, it is 1: 2~2: 1 with the ratio between monomer 1 and the gross mass of monomer 2 to make it, and it is slowly added
Enter into above-mentioned beaker a, stirring is well mixed the liquid in beaker a, and then mixed system is transferred in polymeric kettle, is passed through
Air of the nitrogen to be remained in emptying polymeric kettle, opens stirring, opens fluid temperature liter in polymeric kettle heating system, kettle to be polymerized
At up to 70~95 DEG C, the monomer 1 containing initiator in beaker b is added drop-wise in polymeric kettle dropwise, time for adding control 10~
Within 60min, after completion of dropwise addition, continue to react 1~4h, take out gum-like product, be washed with deionized more than once, remove not
The monomer and oligomer of reaction, are dried after 48~96h in vacuum drier under the conditions of 40~80 DEG C, in high speed disintegrator
It is fully ground, polymer powder is made, and seal standby；
The monomer 1 is one kind in acrylic acid, methacrylic acid, maleic anhydride；
The monomer 2 is one kind in hydroxyethyl methacrylate, hydroxy propyl methacrylate；
The initiator be benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, TBHP,
One kind in cumyl peroxide, di-t-butyl peroxide；
(2) wet spinning technology：Certain mass deionized water is weighed, is placed in suitable beaker, certain matter is weighed
Water soluble alkali is measured, the mass ratio for making water soluble alkali and deionized water is 0.0001: 9.9999~9.5000: 0.5000, 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) obtained polymer powder in, the mass ratio for making polymer and above-mentioned solvent is 0.1: 10~3: 10, and polymer is added
Into the above-mentioned beaker containing solvent, magnetic agitation is carried out at 40~80 DEG C, after thing to be polymerized is dissolved completely in solvent, is stopped
Only stir and be cooled to room temperature, spinning solution is made；The deionized water of certain volume is measured, is placed in coagulating bath, is measured
The inorganic acid of certain volume, it is 0.2: 9.8~9.8: 0.2 to make the ratio between volume of inorganic acid and deionized water, and it is slowly fallen
Enter in above-mentioned coagulating bath, stirring makes deionized water and inorganic acid well mixed, naturally cool to room temperature and setting medium is made；Will be poly-
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, after fully drying, you can acquisition is attached with nothing
The fiber of machine hydrochlorate；
The inorganic acid is one kind in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid；
The water soluble alkali is one kind in sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide；
(3) specially treated technique：A techniques, it is attached to remove with obtained fiber in deionized water cyclic washing step (2)
The inorganic acid salt in fiber surface, when the deionized water pH value of washed fiber is close to 7, washed fiber is immersed in one
In the deionized water for determining quality, fiber is fully swelled in deionized water, above-mentioned swollen fiber is placed in vacuum freeze drying
Freezed in equipment, dry, condenser temperature be -80 DEG C~-40 DEG C, cooling time be 12~36h, vacuum be 0Pa~
100Pa, drying time is 12~36h, treats that fiber is fully parched, and being made has loose and porous structure fiber；B techniques, spend from
Obtained fiber in sub- water cyclic washing step (2), 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 and dries 24~96h, weigh certain mass go from
Sub- water, is placed in suitable beaker, then weighs a certain amount of water soluble alkali, and water soluble alkali is added into 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 the water soluble alkali aqueous solution, so that fiber is fully swelled, then uses deionized water cyclic washing
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 kind in sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide；
(4) complexing technique：Certain mass deionized water is weighed, is placed in suitable beaker, then is weighed and deionized water
The soluble ferrite that mass ratio is 0: 10~10: 0, not including two end points, is added it in above-mentioned deionized water, stirring
It is completely dissolved to soluble ferrite；Obtained fiber in step (3) is taken, makes fiber and above-mentioned soluble ferrite aqueous solution matter
The ratio between amount is 0: 10~10: 10, not including 0: 10, and fiber is immersed in the soluble ferrite aqueous solution, at 20~80 DEG C
Under fiber is complexed with iron ion, complexing several seconds~300min after, fiber is taken out from perferrite solution immediately, obtained
There is the fiber of ferrous ion to complexing；
The soluble ferrite is one kind in frerrous chloride, ferrous sulfate, ferrous nitrate；
(5) heat cross-linking technique：The fiber that the complexing that step (4) is obtained has ferrous ion, which is placed in high temperature furnace, carries out hot friendship
Connection, high temperature furnace temperature is 100~300 DEG C, and crosslinking time is 5~80min, and atmosphere can be air, nitrogen and helium in high temperature furnace
The inert gases such as gas, neon, argon gas, nitrogen, xenon, fiber is then taken out, be cooled in natural environment from high temperature furnace
Room temperature, is made threadiness heterogeneous Fenton catalyst.
Compared with prior art products, first, present invention gained fiber morphologically has outstanding advantage, at this stage, different
Phase Fenton catalysts are generally powdered or graininess, and form is single and preparation process is numerous and diverse, after, need to be by mistake
Filter, centrifugation etc. means separating catalyst, otherwise catalyst easily residue in water and cause secondary pollution, application cost is significantly carried
Rise, present invention gained fiber can directly be delivered 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 be reclaimed easily after, be difficult to cause secondary pollution to environment, through drying process, can be used for multiple times, and pole
The earth reduces use cost, and can through weaving or it is non-woven be processed into variform product, different application neck can be met
Demand of the domain to form；Secondly, present invention gained fiber is extremely hydrophilic, and specific surface area is big, and active specy iron ion is in fiber
Part dissipates extremely uniform, therefore with after waste water containing organic matter, being 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 more preferably, in addition, with same type wet method
Fenton catalysts are compared made from spin processes fiber, when being complexed ferrous ion, and present invention gained fiber has loose
Loose structure, can load more iron ions within the extremely short 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 is difficult to flee from fibrous inside, and iron ion elution amount is drastically reduced when causing application, and reusability is significantly carried
Height, because elution amount is strongly reduced, fibrous inside has retained a large amount of iron ions, in the case of iron ion is largely present, and can quickly urge
Change oxidant (such as hydrogen peroxide, ozone) and generate a large amount of OH isoreactivities oxygen species, and then efficient oxidation at a terrific speed
Decomposing organic matter, realizes quick, effective purification to water body, in thermal crosslinking treatment, regulates and controls through atmosphere in high temperature furnace, can enter one
Existence form, form, crystal formation of step modification iron species etc., further enhance the catalytic activity of fiber, application prospect is more prominent,
Finally, in the range of applicant retrieves, there is not yet manufacturing fibrous heterogeneous Fenton using technique of the present invention
The pertinent literature report of catalyst.
Embodiment
The present invention is further discussed below with reference to embodiment：A kind of fibrous heterogeneous Fenton that the present invention is designed is urged
The manufacture method (hereinafter referred to as manufacture method) of agent is related to precipitation polymerization, wet spinning, penetrating power lifting, iron ion network
The integrated application of the technologies such as conjunction, heat cross-linking, it is intended to iron when solving existing fibrous Fenton catalysts because of preparation
Ion load efficiency is low, using when iron ion be easily eluted etc. caused by defect reusability difference and because iron species are single
The problems such as caused catalytic activity is weak, is that the water body treatings containing organic matter such as waste water from dyestuff create new material, its technical process or
Step is as follows：
(1) Precipitation Polymerization Process：Two parts of monomers 1 are weighed, is placed in suitable beaker a, b, makes in beaker a respectively
The mass ratio of monomer 1 in monomer 1 and beaker b is 10: 0~0: 10, not including two end points, weighs the monomer 2 of certain mass,
It is 0: 10~4: 6 to make the ratio between gross mass of monomer 2 and two parts of monomers 1, not including 0: 10, and monomer 2 is poured into above-mentioned beaker a
In, the initiator of certain mass is weighed, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and
Add it in above-mentioned beaker a, stirring is dissolved completely in monomer up to initiator, and initiator is weighed again, makes initiator
Quality is 0.2~2% of the mass of monomer 1 in above-mentioned beaker b, and is added to above-mentioned beaker b, stirring until initiator is completely dissolved
In monomer, appropriate amount of deionized water is weighed, it is 1: 2~2: 1 with the ratio between monomer 1 and the gross mass of monomer 2 to make it, and it is slowly added
Enter into above-mentioned beaker a, stirring is well mixed the liquid in beaker a, and then mixed system is transferred in polymeric kettle, is passed through
Air of the nitrogen to be remained in emptying polymeric kettle, opens stirring, opens fluid temperature liter in polymeric kettle heating system, kettle to be polymerized
At up to 70~95 DEG C, the monomer 1 containing initiator in beaker b is added drop-wise in polymeric kettle dropwise, time for adding control 10~
Within 60min, after completion of dropwise addition, continue to react 1~4h, take out gum-like product, be washed with deionized more than once, remove not
The monomer and oligomer of reaction, are dried after 48~96h in vacuum drier under the conditions of 40~80 DEG C, in high speed disintegrator
It is fully ground, polymer powder is made, and seal standby；
(2) wet spinning technology：Certain mass deionized water is weighed, is placed in suitable beaker, certain matter is weighed
Water soluble alkali is measured, the mass ratio for making water soluble alkali and deionized water is 0.0001: 9.9999~9.5000: 0.5000, 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) obtained polymer powder in, the mass ratio for making polymer and above-mentioned solvent is 0.1: 10~3: 10, and polymer is added
Into the above-mentioned beaker containing solvent, magnetic agitation is carried out at 40~80 DEG C, after thing to be polymerized is dissolved completely in solvent, is stopped
Only stir and be cooled to room temperature, spinning solution is made；The deionized water of certain volume is measured, is placed in coagulating bath, is measured
The inorganic acid of certain volume, it is 0.2: 9.8~9.8: 0.2 to make the ratio between volume of inorganic acid and deionized water, and it is slowly fallen
Enter in above-mentioned coagulating bath, stirring makes deionized water and inorganic acid well mixed, naturally cool to room temperature and setting medium is made；Will be poly-
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, after fully drying, you can acquisition is attached with nothing
The fiber of machine hydrochlorate；
(3) specially treated technique：A techniques, it is attached to remove with obtained fiber in deionized water cyclic washing step (2)
The inorganic acid salt in fiber surface, when the deionized water pH value of washed fiber is close to 7, washed fiber is immersed in one
In the deionized water for determining quality, fiber is fully swelled in deionized water, above-mentioned swollen fiber is placed in vacuum freeze drying
Freezed in equipment, dry, condenser temperature be -80 DEG C~-40 DEG C, cooling time be 12~36h, vacuum be 0Pa~
100Pa, drying time is 12~36h, treats fiber abundant thousand thoroughly, being made has loose and porous structure fiber；B techniques, spend from
Obtained fiber in sub- water cyclic washing step (2), 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 and dries 24~96h, weigh certain mass go from
Sub- water, is placed in suitable beaker, then weighs a certain amount of water soluble alkali, and water soluble alkali is added into 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 the water soluble alkali aqueous solution, so that fiber is fully swelled, then uses deionized water cyclic washing
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：Certain mass deionized water is weighed, is placed in suitable beaker, then is weighed and deionized water
The soluble ferrite that mass ratio is 0: 10~10: 0, not including two end points, is added it in above-mentioned deionized water, stirring
It is completely dissolved to soluble ferrite；Obtained fiber in step (3) is taken, makes fiber and above-mentioned soluble ferrite aqueous solution matter
The ratio between amount is 0: 10~10: 10, not including 0: 10, and fiber is immersed in the soluble ferrite aqueous solution, at 20~80 DEG C
Under fiber is complexed with iron ion, complexing several seconds~300min after, fiber is taken out from perferrite solution immediately, obtained
There is the fiber of ferrous ion to complexing；
(5) heat cross-linking technique：The fiber that the complexing that step (4) is obtained has ferrous ion, which is placed in high temperature furnace, carries out hot friendship
Connection, high temperature furnace temperature is 100~300 DEG C, and crosslinking time is 5~80min, and atmosphere can be air, nitrogen and helium in high temperature furnace
The inert gases such as gas, neon, argon gas, Krypton, xenon, fiber is then taken out, be cooled in natural environment from high temperature furnace
Room temperature, is made threadiness heterogeneous Fenton catalyst.
Monomer 1 described in manufacture method of the present invention is one kind in acrylic acid, methacrylic acid, maleic anhydride, by
The polymer of the polymerization generation of monomer 1 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 ferrous ion is securely joined with 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 polymer macromolecule by cross-linked network structure, therefore, the present invention manufacture
Monomer 1 described in method is for ensureing that the fiber of synthesized polymer spinning has complexing ferrous ion function, being simultaneously
Heat cross-linking reaction is provided safeguard.The preferred acrylic acid of monomer 1 described in manufacture method of the present invention, reason is as follows：1. acrylic acid
It is simplest unsaturated carboxylic acid, is also polymerization speed very fast vinyl monomer；2. meeting when methacrylic acid is thermally decomposed
Toxic gas is produced, this gas can be with air formation explosive mixture；3. maleic anhydride has strong impulse smell, and
And it is poisonous, skin and mucous membrane can be stimulated, hypopsia or even blindness are caused when serious；Based on above-mentioned three aspects reason, the present invention
The preferred acrylic acid of monomer 1 described in manufacture method.
Monomer 2 described in manufacture method of the present invention is one kind in hydroxyethyl methacrylate, hydroxy propyl methacrylate,
Only polymerize with monomer 1, system viscosity can increased dramatically in polymerization process, in addition produce implode, it is difficult to obtain molecular weight with
Molecular weight distribution it is suitable can spinning polymerizate, even if obtaining the homopolymer of monomer 1, the homopolymer is dissolved in water, but its water
Solution is difficult to solidify, and extreme difficulties are brought to spinning technique, thus, and the one side of monomer 2 is for improving the polymerization temperature of system
And degree, on the other hand it is for improving the spinning spinnability of 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, the introducing of monomer 2 can be with fix tightly of the reinforcing fiber to ferrous ion
Degree, while the progress also reacted for heat cross-linking provides safeguard.The preferred hydroxyethyl methacrylate of monomer 2 described in manufacture method of the present invention
Ethyl ester, reason is as follows：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 manufacture method of the present invention is benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide,
One kind in TBHP, cumyl peroxide, di-t-butyl peroxide, the principle of selection initiator includes：①
Half-life period appropriate initiator is selected according to polymerization temperature, makes polymerization time moderate, based on the heat-transfer capability of polymeric kettle,
On the premise of ensureing temperature control and avoiding implode, the initiation that the initiator of high activity, i.e. half-life period are shorter should be selected as far as possible
Agent, to improve rate of polymerization, shortens polymerization time, while can reduce polymerization temperature and reduce initiator amount；2. it should also examine
Consider initiator polymer quality is whether there is influence, initiator have nontoxicity, using and storage process in 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 TBHP at 154.5 DEG C is 44.8h, isopropyl benzene hydroperoxide at 125 DEG C half
The phase decline for 21h, half-life period of the azodiisobutyronitrile at 100 DEG C is 0.1h, half-life period of the benzoyl peroxide at 125 DEG C be
0.42h, and temperature reduction Increased Plasma Half-life, temperature rise half life.Polymeric reaction temperature scope of the present invention is
70~95 DEG C, the time is 1~4h, and for the reaction time that said temperature is interval and requires, the half-life period of benzoyl peroxide is equal
It is more suitable, it is ensured that with regard to preferable extent of polymerization can be reached in the polymerization time being related to, and due to benzoyl peroxide category
Low toxicity chemicals, uses and stores comparatively safe, therefore currently preferred initiator is benzoyl peroxide.
Inorganic acid described in manufacture method of the present invention is one kind in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, manufacturer of the present invention
Inorganic acid preferably sulfuric acid described in method, reason is as follows：1. compared with nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid property is stable, does not meet with light
Decompose, it is not volatile, will not deliquescence, have no irritating odor, more conducively industrial implementation；2. compared with nitric acid, hydrochloric acid, phosphoric acid, this
It is short that the obtained polymer solution of invention is frozen into the time used in fibre in sulfuric acid coagulating bath, and fibre forming property is preferably, and receiving filament is
Easily, the inorganic acid preferably sulfuric acid therefore described in manufacture method of the present invention.
Water soluble alkali described in manufacture method of the present invention is in sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide
One kind, the preferred sodium hydroxide of water soluble alkali described in manufacture method of the present invention, reason is as follows：1. with lithium hydroxide, potassium hydroxide
Compare, sodium hydroxide is cheap, be easy to get, more conducively industrial implementation；2. it is poly- in solvent preparation, dissolving compared with barium hydroxide
During compound and swollen fiber, though sodium hydroxide and the carbon dioxide reaction in air, product be it is water miscible, no
Easily remain on fiber, and barium hydroxide and Carbon Dioxide in Air reaction product are water insoluble, 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 manufacture method of the present invention
Change sodium.
Soluble ferrite described in manufacture method of the present invention is one kind in frerrous chloride, ferrous sulfate, ferrous nitrate,
The preferred frerrous chloride of soluble ferrite described in manufacture method of the present invention, reason is as follows：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 manufacture method of the present invention
The preferred frerrous chloride of soluble ferrite.
Specific embodiment is given below, so that the present invention to be described in further detail, but the application claims are not
Limited by specific embodiment.
Embodiment 1
Two parts of acrylic acid are weighed, quality is respectively 11.6667g and 33.3333g, are placed in suitable beaker a, b,
5g hydroxyethyl methacrylates are weighed, hydroxyethyl methacrylate is poured into above-mentioned beaker a, 0.0833g benzoyl peroxides are weighed
Formyl, is added it in above-mentioned beaker a, and stirring is dissolved completely in monomer up to benzoyl peroxide, is weighed again
0.1667g benzoyl peroxides, 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 well mixed the liquid in beaker a, then turns mixed system
Move in polymeric kettle, the air for being passed through nitrogen to be remained in emptying polymeric kettle, open stirring, open polymeric kettle heating system, treat
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, continue to react after 2h, take out gum-like product, be washed with deionized 5 times, remove unreacted
Monomer and oligomer, dry after 96h under the conditions of 80 DEG C in vacuum drier, are fully ground in high speed disintegrator, are made
Polymer powder, and seal standby；38.8g deionized waters are weighed, are placed in suitable beaker, 1.2g hydroxides are weighed
Sodium, is added it in the above-mentioned beaker containing deionized water, and solvent is made after sodium hydroxide is completely dissolved；Weigh 2g above-mentioned
The polymer powder of synthesis, is added a polymer in the above-mentioned beaker containing solvent, and magnetic agitation is carried out at 80 DEG C, waits to gather
Compound is dissolved completely in after solvent, stops stirring and being cooled to room temperature, spinning solution is made；80ml deionized waters are measured, by it
It is placed in coagulating bath, measures the 20ml concentrated sulfuric acids, it is slowly poured into above-mentioned coagulating bath, stirring makes deionized water and the concentrated sulfuric acid
It is well mixed, naturally cool to room temperature and setting medium is made；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, utilized
Peristaltic pump drives above-mentioned spinning solution into polytetrafluoroethylene (PTFE) spinning pack with 0.6ml/min speed, to form dynamic analysis of spinning,
Silk is frozen into 20 DEG C of coagulating baths, after fully drying, you can obtain the fiber for being attached with inorganic acid salt；With deionized water repeatedly
Washing is attached with the fiber of inorganic acid salt, when the deionized water pH value of washed fiber is close to 7, and washed fiber is immersed in
In the deionized water of certain mass, the mass ratio of fiber and deionized water is 0.01: 100, fiber is filled in deionized water
Divide and be swelled, washing swelling time is 30min；The fiber being swelled 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 all condensed into solid-state, condenser temperature is -80
DEG C, cooling time is 24h, and the fiber freezed is sent into vacuum freeze drying box, until fiber is fully parched,
In the process, vacuum freeze drying room vacuum is 0Pa, and drying time is 20h, and being made has loose and porous structure fiber；
7.3765g deionized waters are weighed, are placed in suitable beaker, then weigh 2.2070g frerrous chloride tetrahydrates, are added into
Into above-mentioned deionized water, stirring is completely dissolved to it, and weighing 0.0050g has loose and porous structure fiber, and fiber is soaked
Not in ferrous chloride aqueous solution, fiber is set to be complexed with iron ion at 20 DEG C, after 240min, immediately by fiber from chlorine
Change and taken out in the ferrous aqueous solution, be placed in high temperature furnace carrying out heat cross-linking, high temperature furnace temperature is 200 DEG C, and crosslinking time is
Atmosphere is air in 30min, high temperature furnace, and then fiber is taken out from high temperature furnace, room temperature is cooled in natural environment, is made
Fibrous heterogeneous Fenton catalyst.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 2min methylene blues is up to 97%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, and the clearance of 3min methylene blues reaches
95%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum drying
In machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added, led to
Enter 1min ozone, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution,
The clearance of 40min methylene blue dyes is up to 95%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Take out, be placed in vacuum drier in the blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, take the methylene that 10ml concentration is 20mg/L
The base indigo plant aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th time and is catalyzed and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blue dyes is up to 37%；
Embodiment 2
The present embodiment technical process and parameter are same as Example 1, and the only heat cross-linking time is become by the 30min in embodiment 1
For 15min.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 2min methylene blues is up to 96%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, and the clearance of 5min methylene blues reaches
95%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum drying
In machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added, led to
Enter 1min ozone, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution,
The clearance of 90min methylene blue dyes is up to 72%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Take out, be placed in vacuum drier in the blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, take the methylene that 10ml concentration is 20mg/L
The base indigo plant aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th time and is catalyzed and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blue dyes is up to 18%；
Embodiment 3
The present embodiment technical process and parameter are same as Example 1, and the only heat cross-linking time is become by the 30min in embodiment 1
For 25min.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 2min methylene blues is up to 97%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, the clearance of 10min methylene blues
Up to 96%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum and does
In dry machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added,
1min ozone is passed through, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution
In, the clearances of 60min methylene blue dyes is up to 95%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from Asia
Take out, be placed in vacuum drier in the methyl blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, it is 20mg/L's to take 10ml concentration
Aqueous solution of methylene blue, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th time and is catalyzed and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blue dyes is up to 30%.
Embodiment 4
The present embodiment technical process and parameter are same as Example 1, and the only heat cross-linking time is become by the 30min in embodiment 1
For 45min.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 2min methylene blues is up to 97%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, and the clearance of 4min methylene blues reaches
95%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum drying
In machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added, led to
Enter 1min ozone, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution,
The clearance of 90min methylene blue dyes is up to 92%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Take out, be placed in vacuum drier in the blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, take the methylene that 10ml concentration is 20mg/L
The base indigo plant aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th time and is catalyzed and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blue dyes is up to 23%.
Embodiment 5
The present embodiment technical process and parameter are same as Example 1, and the only heat cross-linking time is become by the 30min in embodiment 1
For 60min.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 2min methylene blues is up to 95%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, and the clearance of 5min methylene blues reaches
95%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum drying
In machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added, led to
Enter 1min ozone, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution,
The clearance of 90min methylene blue dyes is up to 64%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Take out, be placed in vacuum drier in the blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, take the methylene that 10ml concentration is 20mg/L
The base indigo plant aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 6th time and is catalyzed and dry fibrous out-phase
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blue dyes 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
For 100 DEG C.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 2min methylene blues is up to 96%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, the clearance of 90min methylene blues
Up to 91%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum and does
In dry machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added,
1min ozone is passed through, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution
In, the clearances of 90min methylene blue dyes 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
For 150 DEG C.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 2min methylene blues is up to 96%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, the clearance of 60min methylene blues
Up to 95%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum and does
In dry machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added,
1min ozone is passed through, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution
In, the clearances of 90min methylene blue dyes 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
For 250 DEG C.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 40min methylene blues is up to 95%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from Asia
Take out, be placed in vacuum drier in the methyl blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, it is 20mg/L's to take 10ml concentration
Aqueous solution of methylene blue, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blues 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
For 300 DEG C.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 2min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, 15min methylene blues
Clearance is up to 96%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in
In vacuum drier, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added
Hydrogen peroxide, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in
State in solution, the clearances of 90min methylene blues is up to 26%.Embodiment 10
The present embodiment technical process and parameter are same as Example 1, and only fiber is complexed the ferrous ion time in embodiment 1
240min be changed into 60min, the heat cross-linking time is changed into 15min from the 30min in embodiment 1.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 15min methylene blues is up to 96%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, the clearance of 90min methylene blues
Up to 72%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum and does
In dry machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added,
1min ozone is passed through, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution
In, the clearances of 90min methylene blues is up to 22%.
Embodiment 11
Two parts of acrylic acid are weighed, quality is respectively 23.3333g and 16.6667g, are placed in suitable beaker a, b,
10g hydroxyethyl methacrylates are weighed, hydroxyethyl methacrylate is poured into above-mentioned beaker a, 0.1667g benzoyl peroxides are weighed
Formyl, is added it in above-mentioned beaker a, and stirring is dissolved completely in monomer up to benzoyl peroxide, is weighed again
0.0833g benzoyl peroxides, 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 well mixed the liquid in beaker a, then turns mixed system
Move in polymeric kettle, the air for being passed through nitrogen to be remained in emptying polymeric kettle, open stirring, open polymeric kettle heating system, treat
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, continue to react after 2h, take out gum-like product, be washed with deionized 5 times, remove unreacted
Monomer and oligomer, dry after 96h under the conditions of 80 DEG C in vacuum drier, are fully ground in high speed disintegrator, are made
Polymer powder, and seal standby；38g deionized waters are weighed, are placed in suitable beaker, 2g sodium hydroxides are weighed,
Add it in the above-mentioned beaker containing deionized water, solvent is made after sodium hydroxide is completely dissolved；Weigh the above-mentioned conjunctions of 2g
Into 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
Thing is dissolved completely in after solvent, stops stirring and being cooled to room temperature, spinning solution is made；80ml deionized waters are measured, are put
In coagulating bath, the 20ml concentrated sulfuric acids are measured, it is slowly poured into above-mentioned coagulating bath, stirring makes deionized water and the concentrated sulfuric acid mixed
Close uniform, naturally cool to room temperature and setting medium is made；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, using compacted
Dynamic pump drives above-mentioned spinning solution into polytetrafluoroethylene (PTFE) spinning pack with 0.6ml/min speed, to form dynamic analysis of spinning,
Silk is frozen into 20 DEG C of coagulating baths, after fully drying, you can obtain the fiber for being attached with inorganic acid salt；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
In the deionized water for determining quality, the mass ratio of fiber and deionized water is 0.01: 100, makes fiber abundant in deionized water
It is swelled, washing swelling time is 30min；The fiber being swelled 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 all condensed into solid-state, condenser temperature is -80 DEG C,
Cooling time is 24h, and the fiber freezed is sent into vacuum freeze drying box, until fiber is fully parched,
During this, vacuum freeze drying room vacuum is 0Pa, and drying time is 20h, and being made has loose and porous structure fiber；Claim
7.3765g deionized waters are taken, are placed in suitable beaker, then weigh 2.2070g frerrous chloride tetrahydrates, are added it to
In above-mentioned deionized water, stirring is completely dissolved to it, and weighing 0.0050g has loose and porous structure fiber, and fiber is submerged
In ferrous chloride aqueous solution, fiber is set to be complexed with iron ion at 20 DEG C, after 60min, immediately by fiber from chlorination
Taken out in the ferrous aqueous solution, be placed in high temperature furnace carrying out heat cross-linking, high temperature furnace temperature is 200 DEG C, and crosslinking time is 15min,
Atmosphere is air in high temperature furnace, and then fiber is taken out from high temperature furnace, room temperature is cooled in natural environment, and threadiness is made
Heterogeneous Fenton catalyst.
The aqueous solution of methylene blue that 10ml concentration is 20mgL is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by threadiness
Heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by threadiness
Heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, under the conditions of 40 DEG C
1.5h is dried, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, is passed through 1min ozone, will complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying for the first time is placed in above-mentioned solution, the removal of 1min methylene blues
Rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum
In drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l dioxygens are added
Water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned molten
In liquid, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Take out, be placed in vacuum drier in the blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, take the methylene that 10ml concentration is 20mgL
The base indigo plant aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 60min methylene blues is up to 95%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, the clearance of 90min methylene blues
Up to 22%.
Embodiment 12
A acrylic acid is weighed, quality is 35g, be placed in suitable beaker a, weigh 15g hydroxyethyl methacrylate second
Ester, hydroxyethyl methacrylate is poured into above-mentioned beaker a, 0.25g benzoyl peroxides are weighed, above-mentioned beaker is added it to
In a, stirring is dissolved completely in monomer up to benzoyl peroxide, is weighed 50g deionized waters, is slowly added into above-mentioned burning
In cup a, stirring is well mixed the liquid in beaker a, and then mixed system is transferred in polymeric kettle, nitrogen is passed through with emptying
The air remained in polymeric kettle, opens stirring, opens fluid temperature in polymeric kettle heating system, kettle to be polymerized and is increased to 85 DEG C
When, start after timing, reaction 2.5h, take out gum-like product, be washed with deionized 5 times, remove unreacted monomer and low
Polymers, dries after 96h under the conditions of 80 DEG C in vacuum drier, is fully ground in high speed disintegrator, and powdered polymeric is made
Thing, and seal standby；32g deionized waters are weighed, are placed in suitable beaker, 8g sodium hydroxides 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, is added a polymer in the above-mentioned beaker containing solvent, and magnetic agitation is carried out at 80 DEG C, and thing to be polymerized is completely dissolved
In after solvent, stopping stirring and being cooled to room temperature, spinning solution is made；80ml deionized waters are measured, are placed in coagulating bath,
The 20ml concentrated sulfuric acids are measured, it is slowly poured into above-mentioned coagulating bath, stirring makes deionized water and the concentrated sulfuric acid well mixed, natural
It is cooled to room temperature and setting medium is made；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, will be above-mentioned using peristaltic pump
Spinning solution is driven into polytetrafluoroethylene (PTFE) spinning pack with 0.6ml/min speed, to form dynamic analysis of spinning, in 20 DEG C of coagulating baths
In be frozen into silk, after fully drying, you can obtain and be attached with the fiber of inorganic acid salt；Nothing is attached with deionized water cyclic washing
The fiber of machine hydrochlorate, when the deionized water pH value of washed fiber is close to 7, going for certain mass is immersed in by washed fiber
In ionized water, the mass ratio of fiber and deionized water is 0.01: 100, fiber is fully swelled in deionized water, is washed molten
The swollen time is 30min；The fiber being swelled is put into freeze-drying pallet, and this pallet is placed in vacuum freeze
In cold-trap, it is freezed, fiber contained humidity is all condensed into solid-state, condenser temperature is -80 DEG C, and cooling time is
24h, the fiber freezed is sent into vacuum freeze drying box, until fiber is fully parched, in the process, very
Vacuum freecing-dry room vacuum is 0Pa, and drying time is 20h, and being made has loose and porous structure fiber；7.3765g is weighed to go
Ionized water, is placed in suitable beaker, then weighs 2.2070g frerrous chloride tetrahydrates, adds it to above-mentioned deionization
In water, stirring is completely dissolved to it, and weighing 0.0050g has loose and porous structure fiber, and fiber is immersed in into frerrous chloride
In the aqueous solution, fiber is set to be complexed with iron ion at 20 DEG C, after 60min, immediately by fiber from ferrous chloride aqueous solution
It is middle to take out, it is placed in high temperature furnace carrying out heat cross-linking, high temperature furnace temperature is 200 DEG C, and crosslinking time is gas in 15min, high temperature furnace
Atmosphere is air, and then fiber is taken out from high temperature furnace, room temperature is cooled in natural environment, and threadiness heterophase Fenton is made
Catalysts.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 2min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 40min methylene blues is up to 95%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from Asia
Take out, be placed in vacuum drier in the methyl blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, it is 20mg/L's to take 10ml concentration
Aqueous solution of methylene blue, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blues is up to 23%.
Embodiment 13
A acrylic acid is weighed, quality is 30g, be placed in suitable beaker a, weigh 20g hydroxyethyl methacrylate second
Ester, hydroxyethyl methacrylate is poured into above-mentioned beaker a, 0.25g benzoyl peroxides are weighed, above-mentioned beaker is added it to
In a, stirring is dissolved completely in monomer up to benzoyl peroxide, is weighed 50g deionized waters, is slowly added into above-mentioned burning
In cup a, stirring is well mixed the liquid in beaker a, and then mixed system is transferred in polymeric kettle, nitrogen is passed through with emptying
The air remained in polymeric kettle, opens stirring, opens fluid temperature in polymeric kettle heating system, kettle to be polymerized and is increased to 85 DEG C
When, start after timing, reaction 2.5h, take out gum-like product, be washed with deionized 5 times, remove unreacted monomer and low
Polymers, dries after 96h under the conditions of 80 DEG C in vacuum drier, is fully ground in high speed disintegrator, and powdered polymeric is made
Thing, and seal standby；32g deionized waters are weighed, are placed in suitable beaker, 8g sodium hydroxides 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, is added a polymer in the above-mentioned beaker containing solvent, and magnetic agitation is carried out at 80 DEG C, and thing to be polymerized is completely dissolved
In after solvent, stopping stirring and being cooled to room temperature, spinning solution is made；80ml deionized waters are measured, are placed in coagulating bath,
The 20ml concentrated sulfuric acids are measured, it is slowly poured into above-mentioned coagulating bath, stirring makes deionized water and the concentrated sulfuric acid well mixed, natural
It is cooled to room temperature and setting medium is made；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, will be above-mentioned using peristaltic pump
Spinning solution is driven into polytetrafluoroethylene (PTFE) spinning pack with 0.6ml/min speed, to form dynamic analysis of spinning, in 20 DEG C of coagulating baths
In be frozen into silk, after fully drying, you can obtain and be attached with the fiber of inorganic acid salt；Nothing is attached with deionized water cyclic washing
The fiber of machine hydrochlorate, when the deionized water pH value of washed fiber is close to 7, going for certain mass is immersed in by washed fiber
In ionized water, the mass ratio of fiber and deionized water is 0.01: 100, fiber is fully swelled in deionized water, is washed molten
The swollen time is 30min；The fiber being swelled is put into freeze-drying pallet, and this pallet is placed in vacuum freeze
In cold-trap, it is freezed, fiber contained humidity is all condensed into solid-state, condenser temperature is -80 DEG C, and cooling time is
24h, the fiber freezed is sent into vacuum freeze drying box, until fiber is fully parched, in the process, very
Vacuum freecing-dry room vacuum is 0Pa, and drying time is 20h, and being made has loose and porous structure fiber；7.3765g is weighed to go
Ionized water, is placed in suitable beaker, then weighs 2.2070g frerrous chloride tetrahydrates, adds it to above-mentioned deionization
In water, stirring is completely dissolved to it, and weighing 0.0050g has loose and porous structure fiber, and fiber is immersed in into frerrous chloride
In the aqueous solution, fiber is set to be complexed with iron ion at 20 DEG C, after 60min, immediately by fiber from ferrous chloride aqueous solution
It is middle to take out, it is placed in high temperature furnace carrying out heat cross-linking, high temperature furnace temperature is 200 DEG C, and crosslinking time is gas in 15min, high temperature furnace
Atmosphere is air, and then fiber is taken out from high temperature furnace, room temperature is cooled in natural environment, and threadiness heterophase Fenton is made
Catalysts.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 5min methylene blues are gone
Except rate is up to 95%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 90min methylene blues is up to 85%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from Asia
Take out, be placed in vacuum drier in the methyl blue aqueous solution, 1.5h is dried under the conditions of 40 DEG C, it is 20mg/L's to take 10ml concentration
Aqueous solution of methylene blue, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blues is up to 22%.
Embodiment 14
Two parts of acrylic acid are weighed, quality is respectively 11.6667g and 33.3333g, are placed in suitable beaker a, b,
5g hydroxyethyl methacrylates are weighed, hydroxyethyl methacrylate is poured into above-mentioned beaker a, 0.0833g benzoyl peroxides are weighed
Formyl, is added it in above-mentioned beaker a, and stirring is dissolved completely in monomer up to benzoyl peroxide, is weighed again
0.1667g benzoyl peroxides, 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 well mixed the liquid in beaker a, then turns mixed system
Move in polymeric kettle, the air for being passed through nitrogen to be remained in emptying polymeric kettle, open stirring, open polymeric kettle heating system, treat
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, continue to react after 2h, take out gum-like product, be washed with deionized 5 times, remove unreacted
Monomer and oligomer, dry after 96h under the conditions of 80 DEG C in vacuum drier, are fully ground in high speed disintegrator, are made
Polymer powder, and seal standby；38.8g deionized waters are weighed, are placed in suitable beaker, 1.2g hydroxides are weighed
Sodium, is added it in the above-mentioned beaker containing deionized water, and solvent is made after sodium hydroxide is completely dissolved；Weigh 2g above-mentioned
The polymer powder of synthesis, is added a polymer in the above-mentioned beaker containing solvent, and magnetic agitation is carried out at 80 DEG C, waits to gather
Compound is dissolved completely in after solvent, stops stirring and being cooled to room temperature, spinning solution is made；80ml deionized waters are measured, by it
It is placed in coagulating bath, measures the 20ml concentrated sulfuric acids, it is slowly poured into above-mentioned coagulating bath, stirring makes deionized water and the concentrated sulfuric acid
It is well mixed, naturally cool to room temperature and setting medium is made；Polytetrafluoroethylene (PTFE) spinning pack is immersed in coagulation bath, utilized
Peristaltic pump drives above-mentioned spinning solution into polytetrafluoroethylene (PTFE) spinning pack with 0.6ml/min speed, to form dynamic analysis of spinning,
Silk is frozen into 20 DEG C of coagulating baths, after fully drying, you can obtain the fiber for being attached with inorganic acid salt；With deionized water repeatedly
Washing is attached with the fiber of inorganic acid salt, when the deionized water pH value of washed fiber is close to 7, and washed fiber is placed in certainly
24h is dried under right environment, 9.990g deionized waters is weighed, is placed in suitable beaker, then weighs 0.0100g sodium hydroxides,
Add it in above-mentioned deionized water, stirring is completely dissolved to sodium hydroxide, weighs the fiber of 0.0050g natural air dryings, and
Fiber is immersed in sodium hydrate aqueous solution, fiber is swelled at 20 DEG C, after being swelled through 60min, with deionized water repeatedly
Fiber is washed, until the deionized water pH value of washed fiber is close to 7, being made has loose and porous structure fiber；Weigh
7.3765g deionized waters, are placed in suitable beaker, then weigh 2.2070g frerrous chloride tetrahydrates, add it to
State in deionized water, stir 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
Carry out heat cross-linking in high temperature furnace, high temperature furnace temperature is 200 DEG C, crosslinking time is that atmosphere is air in 30min, high temperature furnace, then
Fiber is taken out from high temperature furnace, room temperature is cooled in natural environment, threadiness heterogeneous Fenton catalyst is made.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 1min methylene blues is up to 97%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 3min methylene blues is up to 97%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, the clearance of 90min methylene blues
Up to 88%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in vacuum and does
In dry machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide are added,
1min ozone is passed through, the fibrous heterogeneous Fenton catalyst that will be completed the 5th catalysis and dry is placed in above-mentioned solution
In, the clearances of 90min methylene blue dyes is up to 18%.
Embodiment 15
The present embodiment technical process and parameter are identical with embodiment 14, and only heat cross-linking temperature is by 200 DEG C of changes in embodiment 1
For 300 DEG C.
The aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l hydrogen peroxide is added, 1min ozone is passed through, by fiber
Shape heterogeneous Fenton catalyst is placed in above-mentioned solution, and the blue clearance of 1min methylenes is 97%；Now, by fiber
Shape heterogeneous Fenton catalyst is rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, in 40 DEG C of conditions
Lower dry 1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will be complete
The fibrous heterogeneous Fenton catalyst for being catalyzed and drying into first time is placed in above-mentioned solution, and 1min methylene blues are gone
Except rate is up to 97%；Now, by the rapid taking-up from aqueous solution of methylene blue of fibrous heterogeneous Fenton catalyst, it is placed in true
In empty drying machine, 1.5h is dried under the conditions of 40 DEG C, the aqueous solution of methylene blue that 10ml concentration is 20mg/L is taken, 2 μ l are added double
Oxygen water, is passed through 1min ozone, and the fibrous heterogeneous Fenton catalyst that will be completed second of catalysis and dry is placed in above-mentioned
In solution, the clearances of 4min methylene blues is up to 96%；Now, it is fibrous heterogeneous Fenton catalyst is rapid from methylene
Taken out in the base indigo plant aqueous solution, be placed in vacuum drier, 1.5h is dried under the conditions of 40 DEG C, take the Asia that 10ml concentration is 20mg/L
The methyl blue aqueous solution, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the fibrous out-phase that third time is catalyzed and dried
Fenton catalysts are placed in above-mentioned solution, and the clearances of 90min methylene blues is up to 82%；Now, by fibrous out-phase
Fenton catalysts are rapid to be taken out from aqueous solution of methylene blue, is placed in vacuum drier, is dried under the conditions of 40 DEG C
1.5h, takes the aqueous solution of methylene blue that 10ml concentration is 20mg/L, adds 2 μ l hydrogen peroxide, is passed through 1min ozone, will complete the 4th
The secondary fibrous heterogeneous Fenton catalyst for being catalyzed and drying is placed in above-mentioned solution, the clearance of 90min methylene blues
Up to 19%.
Claims (7)
1. a kind of manufacture method of fibrous heterogeneous Fenton catalyst, it is characterised in that technical process is as follows：
(1) Precipitation Polymerization Process：Two parts of monomers 1 are weighed, is placed on respectively in suitable beaker a, b, makes the monomer in beaker a
1 is 10: 0~0: 10 with the mass ratio of monomer 1 in beaker b, not including two end points, weighs the monomer 2 of certain mass, makes list
The ratio between gross mass of body 2 and two parts of monomers 1 is 0: 10~4: 6, not including 0: 10, and monomer 2 is poured into above-mentioned beaker a, is claimed
The initiator of certain mass is taken, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and added
Enter into above-mentioned beaker a, stirring weighs initiator, make the initiator quality be until initiator is dissolved completely in monomer again
The 0.2~2% of the mass of monomer 1 in above-mentioned beaker b, and above-mentioned beaker b, stirring are added to until initiator is dissolved completely in monomer
In, appropriate amount of deionized water is weighed, it is 1: 2~2: 1 with the ratio between monomer 1 and the gross mass of monomer 2 to make it, and is slowly added into
State in beaker a, stirring is well mixed liquid in beaker a, and then mixed system is transferred in polymeric kettle, be passed through nitrogen with
The air remained in emptying polymeric kettle, opens stirring, opens fluid temperature in polymeric kettle heating system, kettle to be polymerized and is increased to 70
At~95 DEG C, the monomer 1 containing initiator in beaker b is added drop-wise in polymeric kettle dropwise, time for adding control 10~60min it
It is interior, after completion of dropwise addition, continue to react 1~4h, take out gum-like product, be washed with deionized more than once, remove unreacted
Monomer and oligomer, dry after 48~96h under the conditions of 40~80 DEG C in vacuum drier, are fully ground in high speed disintegrator
Mill, is made polymer powder, and seal standby；
(2) wet spinning technology：Certain mass deionized water is weighed, is placed in suitable beaker, weighing certain mass can
Dissolubility alkali, the mass ratio for making water soluble alkali and deionized water is 0.0001: 9.9999~9.5000: 0.5000, is added into
Into the above-mentioned beaker containing deionized water, solvent is made after water soluble alkali is completely dissolved；Weigh in certain mass step (1)
Obtained polymer powder, the mass ratio for making polymer and above-mentioned solvent is 0.1: 10~3: 10, is added a polymer to
State in the beaker containing solvent, magnetic agitation is carried out at 40~80 DEG C, after thing to be polymerized is dissolved completely in solvent, stop stirring
Mix and be cooled to room temperature, spinning solution is made；The deionized water of certain volume is measured, is placed in coagulating bath, is measured certain
The inorganic acid of volume, it is 0.2: 9.8~9.8: 0.2 to make the ratio between volume of inorganic acid and deionized water, and it is slowly poured into
State in coagulating bath, stirring makes deionized water and inorganic acid well mixed, naturally cool to room temperature and setting medium is made；By polytetrafluoro
Ethene 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, after fully drying, you can acquisition is attached with inorganic acid
The fiber of salt；
(3) specially treated technique：A techniques, with obtained fiber in deionized water cyclic washing step (2), are attached to removing
The inorganic acid salt of fiber surface, when the deionized water pH value of washed fiber is close to 7, certain matter is immersed in by washed fiber
In the deionized water of amount, fiber is fully swelled in deionized water, above-mentioned swollen fiber is placed in vacuum freeze
Middle to be freezed, dried, condenser temperature is -80 DEG C~-40 DEG C, and cooling time is 12~36h, and vacuum is 0Pa~100Pa,
Drying time is 12~36h, treats that fiber is fully parched, and being made has loose and porous structure fiber；B techniques, it is anti-with deionized water
Obtained fiber 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 and dries 24~96h, the deionized water of certain mass is weighed, 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 the water soluble alkali aqueous solution, so that fiber is fully swelled, deionized water cyclic washing fiber is then used, 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：Certain mass deionized water is weighed, is placed in suitable beaker, then is weighed and deionized water quality
Than the soluble ferrite for 0: 10~10: 0, not including two end points, add it in above-mentioned deionized water, stirring extremely may be used
Dissolubility ferrous salt is completely dissolved；Take in step (3) obtained fiber, make fiber and above-mentioned soluble ferrite aqueous solution quality it
Than for 0: 10~10: 10, not including 0: 10, and fiber being immersed in the soluble ferrite aqueous solution, being made at 20~80 DEG C
Fiber is complexed with iron ion, after several seconds~300min of complexing, fiber is taken out from perferrite solution immediately, network is obtained
Close the fiber for having ferrous ion；
(5) heat cross-linking technique：The fiber that the complexing that step (4) is obtained has ferrous ion, which is placed in high temperature furnace, 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 and helium,
The inert gases such as neon, argon gas, Krypton, xenon, fiber is then taken out, room is cooled in natural environment from high temperature furnace
Temperature, is made threadiness heterogeneous Fenton catalyst.
2. a kind of manufacture method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
Described monomer 1 is one kind in acrylic acid, methacrylic acid, maleic anhydride；Monomer 2 be hydroxyethyl methacrylate,
One kind in hydroxy propyl methacrylate.
3. a kind of manufacture method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
Described initiator is benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, TBHP, peroxidating
One kind in diisopropylbenzene (DIPB), di-t-butyl peroxide.
4. a kind of manufacture method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
Described inorganic acid is one kind in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid.
5. a kind of manufacture method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
Described water soluble alkali is one kind in sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide.
6. a kind of manufacture method of fibrous heterogeneous Fenton catalyst according to claim 1, it is characterised in that
Described soluble ferrite is one kind in frerrous chloride, ferrous sulfate, ferrous nitrate.
7. according to a kind of manufacture method of fibrous heterogeneous Fenton catalyst according to any one of claims 1 to 6,
It is characterized in that described monomer 1 is acrylic acid, described monomer 2 is hydroxyethyl methacrylate, and described initiator was
BP, described inorganic acid is sulfuric acid, and described water soluble alkali is sodium hydroxide, and described soluble ferrite is chlorine
Change ferrous.
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