CN105056949B - A kind of fiber-loaded type Fenton catalyst of plant hollow, preparation method and applications - Google Patents
A kind of fiber-loaded type Fenton catalyst of plant hollow, preparation method and applications Download PDFInfo
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- CN105056949B CN105056949B CN201510482108.3A CN201510482108A CN105056949B CN 105056949 B CN105056949 B CN 105056949B CN 201510482108 A CN201510482108 A CN 201510482108A CN 105056949 B CN105056949 B CN 105056949B
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Abstract
The invention discloses a kind of fiber-loaded type Fenton catalyst of plant hollow, preparation method and applications, including carrier and be carried on supported catalyst；Described carrier is plant hollow fiber, and described catalyst is heterogeneous type Fenton catalyst；The carrier that platanus fruit wool fibre is heterogeneous type Fenton catalyst has innovatively been selected to originate, the fiber is natural reproducible resource, wide material sources, easily biological-degradable, as type Fenton catalyst carrier and applied to the degraded of pollutant in water body, realize the treatment of wastes with processes of wastes against one another of composite Materials Design and application, environmental protection；Ferroso-ferric oxide type Fenton catalyst is loaded by the platanus fruit wool fibre obtained by simple step and gentle experiment condition, it is excellent to the catalytic effect of methylene blue dye wastewater, experimental data confirms the high recycling rate of the material, has broad application prospects.
Description
Technical field
The invention belongs to field of compound material, it is catalyzed more particularly, to a kind of fiber-loaded Fenton-like of plant hollow
Agent, preparation method and applications.
Background technology
The water pollution of current China is increasingly severe, wherein the Wastewater Dyes molecule content that modern printing and dyeing industry is discharged
Exceeded, printing and dyeing molecule is difficult to degrade, and health and ecological environment are caused a significant threat, therefore is had to the processing of dyeing waste water
There is important theory and practice meaning.The method of processing dyeing waste water mainly has at present：Absorption method, membrane separation process, chemical coagulation
Method, photocatalytic oxidation, wet air oxidation, biochemical process, Fenton reagent oxidizing process etc..Wherein, Fenton reagent method is
H2O2In Fe2+Catalytic action under generation with high reaction activity hydroxyl radical free radical (OH), OH can with it is most of organic
Thing effect makes it degrade.Based on the improvement to traditional Fenton methods, research discovery utilizes Fe3+、Mn2+Deng homogeneous catalyst and iron
The heterogeneous catalysis such as powder, graphite, iron, the oxide mineral of manganese are shared, and can equally make H2O2Decompose and produce OH, because of its reactive group
This process is similar with Fenton catalyst, therefore referred to as type Fenton catalyst.It is simple that type Fenton catalyst method invests small, technique
It is single, easy to operate, it has been increasingly becoming one of focus of field of waste water treatment research.
In numerous modified Fenton reactions, Fe3O4Due to Fe can coexist in heterogeneous system2+With Fe3+, can be effectively
Gathering and precipitating for homogeneous Fe is avoided, and its magnetic brings very big facility for the separation of catalyst, therefore, Fe3O4It is current
One of ideal type Fenton catalyst.Research shows, by suitable carrier can realize the absorption of heterogeneous catalysis-
Synergy between advanced oxidation, can effectively improve Fe3O4Advanced oxidation efficiency.At present by activated carbon, zeolite,
The materials such as clay are as carrier, applied to Fe3O4The load and preparation of type Fenton catalyst, still, these materials are all often
The irregular powder of size or particle diameter larger block fragment, particle etc., with certain limitation, are unfavorable for practical application.
In recent years in, also occur in that and regard the material of the hollow tubular structures such as CNT and chitosan conduit as Fe3O4Type Fenton catalyst
The research report of carrier, but they are required for the surface chemical modification of special carrier preparation technology and carrier, complex operation and
Cost is higher, also greatly constrains this class support type Fe3O4The preparation and application of type Fenton catalyst.
Plane tree system Platanaceae plane fallen leaves megaphanerophyte, originates in North America, Mexico, Mediterranean and the band of India one.
Plane tree is a ball, two balls, sycamore with the plane tree for Shade Trees, China in many cities of China.It is outstanding
Suzuki cone maturation rear overhang is hung on tree not fall through the winter, next spring carpopodium fracture, and cone drops in ground, by mechanical force consequence
Ball is burst, and shed many pyrenes, and the fruit that is born on pyrene hair descends slowly and lightly everywhere, then severe contamination air in many ways
And human settlement：First, it is broken repeatedly by mechanical force after platanus fruit hair landing, forms pellet
(PM10) discomfort, is caused to human eye nose, pruitus and keratitis can be caused；Second, platanus fruit hair is adsorbed with bacterium and disease
Poison, enters after human body with fruit hair chip, triggers the diseases such as respiratory tract infection, asthma, cough to seriously endanger health；3rd,
The platanus fruit hair of ground and accumulation of being scattered brings pressure for the cleaning in city, flies away skyborne platanus fruit hair and also can
Interference driving driving sight, influences traffic.Therefore, the pollution of platanus fruit hair allows people to complain incessantly and have no way out always.
In fact, distressful platanus fruit hair for a long time, is a kind of excellent natural fiber, the smooth nothing of the fiber surface in itself
Pleat, in hollow structure, wall is thin, and specific surface area is big, platanus fruit wool fibre by pectin, cellulose and lignin constitute it is dead thin
Born of the same parents' linear array is formed, and matter is hard, is difficult compressive deformation., can be fully sharp if platanus fruit hair collected and development of resources
With advantages such as the stable and unique tubular structures of its widely distributed, performance, a series of new material developed will have
Considerable economic benefit and it is widely applied prospect.At present, only Ma Yanwen etc. is on the quilted standby carbon micron of carbonization oriental plane tree
Manage and as the research of electrode of super capacitor, and there is not yet any utilization platanus fruit hair prepares support type Fe3O4Class
The report of Fenton catalyst.
The content of the invention
For defect of the prior art and deficiency, it is an object of the invention to provide a kind of fiber-loaded class of plant hollow
Fenton catalyst, preparation method and applications, solve in the prior art complex operation, the problem of cost is high.
To solve the above problems, the technical solution adopted in the present invention is：
A kind of fiber-loaded type Fenton catalyst of plant hollow, including carrier and it is carried on supported catalyst；
Described carrier is plant hollow fiber, and described catalyst is heterogeneous type Fenton catalyst.
Specifically, described plant hollow fiber is platanus fruit wool fibre, the external diameter of platanus fruit wool fibre for 25~
30 μm, the internal diameter of platanus fruit wool fibre is 20~28 μm；Described heterogeneous type Fenton catalyst is ferroso-ferric oxide, molybdenum
Sour iron or ferric sulfate；Described is carried on supported catalyst thickness for 2~5 μm.
Specifically, described ferroso-ferric oxide is ferroferric oxide nano granules, the particle diameter of ferroferric oxide nano granules
For 35~60nm.
The method for preparing the fiber-loaded type Fenton catalyst of described plant hollow, including by trivalent iron salt, reduction
Sediment is obtained by hydro-thermal reaction after plant hollow fiber and stabilizer mixing after agent, cleaning, then sediment is carried out clearly
Wash and be drying to obtain the fiber-loaded type Fenton catalyst of plant hollow.
Specifically, described trivalent iron salt and the use magnitude relation of reducing agent, which are 0.1~2g trivalent iron salts, adds 5ml reduction
Platanus fruit wool fibre after agent, described trivalent iron salt and cleaning is that 5~20g trivalent iron salts add 1g and cleaned with magnitude relation
The trivalent iron salt addition 1 that platanus fruit wool fibre afterwards, described trivalent iron salt and the use magnitude relation of stabilizer are 0.1~2g~
5ml stabilizer；
Described trivalent iron salt is ferric trichloride, ferric sulfate or ferric nitrate, and described reducing agent is hydrazine hydrate, described
Stabilizer is formaldehyde.
More specifically, the condition of described hydro-thermal reaction is that 2~8h is reacted at a temperature of 110~150 DEG C.
In addition, described drying is 40~80 DEG C of vacuum drying, drying time is 4~12h.
The fiber-loaded type Fenton catalyst of described plant hollow is used to be catalyzed methylene blue degradation of dye effluent
Using.
Compared with prior art, the beneficial effects of the invention are as follows：
Plant hollow has been made from natural platanus fruit wool fibre using friendly reaction and build environment in the present invention
Fiber-loaded ferroso-ferric oxide type Fenton catalyst；
First, innovatively select the carrier that platanus fruit wool fibre is heterogeneous type Fenton catalyst to originate, should
Fiber is used as renewable resource, wide material sources, easily biological-degradable, using it as the carrier of type Fenton catalyst and applied to water
The degraded of pollutant in body, realizes the treatment of wastes with processes of wastes against one another of composite Materials Design and application, environmental protection；
Second, platanus fruit hair is tubular structure, the Fe of the structural load3O4Resulting type Fenton catalyst tool
There is specific surface area big, the advantage of high adsorption capacity.By means of the huge cavity of the material internal, pollutant point in water body can be achieved
Son, in the efficient absorption and storage of material surface and cavity inside, is then that next step occurs in load by means of diffusion and mass transfer
The Fenton catalysis on state ferroso-ferric oxide surface provides the prerequisite acted synergistically between absorption-advanced oxidation；
3rd, pass through the fiber-loaded ferroso-ferric oxide of plant hollow obtained by simple step and gentle experiment condition
Type Fenton catalyst, excellent to the catalytic effect of methylene blue dye wastewater, experimental data confirms the repetition of the material
Utilization rate is high, has broad application prospects；
4th, the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow prepared has magnetic, very
It is easy to separation, it is easy to operate, secondary pollution will not be caused to environment.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the catalyst that example IV is prepared；
Fig. 2 is the power spectrum measure figure for the catalyst that example IV is prepared；
Fig. 3 is the X-ray diffractogram for the catalyst that example IV is prepared；
Fig. 4 is the infrared spectrogram for the catalyst that example IV is prepared；
Fig. 5 is the hysteresis graph for the catalyst that example IV is prepared；
Fig. 6 is Fenton catalytic degradation of the catalyst for preparing of example IV to methylene blue stimulated dye wastewater
Figure, the catalyst that 1,2,3,4 example IV when being 60,90,120,30min is prepared is to the blue solution degradation crest of subunit；
Fig. 7 is the recycling figure for the catalyst that example IV is prepared；
The present invention is described in further detail with reference to Figure of description and embodiment.
Embodiment
Involved technical scheme and method in the present invention, are applicable not only to the platanus fruit hair doughnut load four
The preparation of Fe 3 O type Fenton catalyst, can also be used for reference and applied to other natural fiber materials as basic syntheti c route
The preparation of material load heterogeneous Fenton catalyst or type Fenton catalyst.Loaded in other natural fiber materials heterogeneous
In the preparation of Fenton catalyst or type Fenton catalyst：On the one hand, natural fiber material species is chosen as root system of plant, fibre
Tie up beam, pistil, fruit hair, fine hair etc.；On the other hand it can realize that catalyst optional iron molybdate, the ferric sulfate of load etc. are common
Fenton catalyst or type Fenton catalyst material, possible other natural fiber materials load heterogeneous Fenton of the above are urged
The preparation of agent or type Fenton catalyst, only need to be in preparation according to the source of natural fiber material, basic characteristics and poor performance
It is different, and the specific preparation condition that other Fenton catalysis or the preparation of type Fenton catalyst material are synthesized, make to adjust
Obtain a variety of natural fiber materials load heterogeneous Fenton catalyst or Fenton-like based on basic syntheti c route of the invention
Catalyst material.
Heterogeneous type Fenton catalyst of the present invention includes iron molybdate, ferroso-ferric oxide and ferric sulfate etc.；This hair
Bright described heterogeneous Fenton catalyst is including ferrous sulfate etc..
The specific present invention carries out load ferroso-ferric oxide type Fenton catalyst, the party by taking platanus fruit wool fibre as an example
It is outstanding with hollow tubular structures inside the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow obtained by method
Suzuki fruit wool fibre, and the outside Fe for load3O4Layer.Specifically, the fiber-loaded ferroso-ferric oxide class of described plant hollow
Fenton catalyst is micron tubular pattern, and external diameter is about 25-30 μm, about 2-5 μm of ferroso-ferric oxide load layer thickness, and internal diameter is about
For 20-28 μm, inside has very big cavity area, and the material surface is coarse, the ferroso-ferric oxide for being about 35-60nm by particle diameter
Nano particle is constituted.
The fiber-loaded Fenton catalyst of plant hollow shows excellent in the degraded of methylene blue stimulated dye wastewater
Different catalytic degradation performance.Platanus fruit hair doughnut load type Fenton catalyst of the present invention is applied to
When in Fenton catalytic reactions, the material outer layer ferroso-ferric oxide can effectively play catalytic activity, internal platanus fruit
Hair doughnut can aid in playing the effect of absorption mass transfer simultaneously, be conducive to the reality acted synergistically between absorption-advanced oxidation
It is existing.Therefore, platanus fruit hair doughnut load type Fenton catalyst unique structure design and preparation method, in realizing
Layer materials cleverly coupling and performance superposition on functional plane, can be achieved the collaboration of absorption-advanced oxidation in hollow structure
Effect, effectively increases the platanus fruit hair fiber-loaded type Fenton catalyst of plant hollow in methylene blue stimulated dye wastewater
Fenton advanced oxidation degradation efficiency.
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The preparation process of the platanus fruit hair doughnut load type Fenton catalyst of the present invention is as follows：
1st, the washing of platanus fruit wool fibre：Platanus fruit wool fibre is weighed to add by every 50~200g fibers with detergent
The ratio of 3~10L ethanol is mixed in container, stirs at room temperature after 0.5~1h, liquid is filtered off in vavuum pump, is repeated
This operation three times, realizes abundant cleaning of the detergent to platanus fruit wool fibre, obtains refined platanus fruit wool fibre；
Above-mentioned detergent is ethanol or deionized water；
2nd, platanus fruit wool fibre loads the generation of ferriferrous oxide composite material：0.5~2g trivalent iron salts are weighed in appearance
In device, 5ml hydrazine hydrates are added, stirring 0.5~4h at 30~80 DEG C with magnetic stirring apparatus is completely dissolved it and adds 0.1g
The refined platanus fruit wool fibre that step 1 is prepared, is stirred at 30~80 DEG C with magnetic stirring apparatus and outstanding bell is added after 2~5h
Wooden fruit wool fibre, formaldehyde is added after being sufficiently stirred for is well mixed it, and above-mentioned solution is added in 50ml pyroreaction kettles,
2~8h is reacted in 110~150 DEG C of baking oven, hydrazine hydrate is added in above-mentioned system and causes making for ferric trichloride and hydrazine hydrate
With than using 5mL hydrazine hydrates for every 0.1~2g ferric trichlorides.Reactor reaction temperature is 110~150 DEG C, magnetic agitation temperature
Spend for 30~80 DEG C of 2~5h of stirring；
Described trivalent iron salt can be ferric trichloride, ferric sulfate or ferric nitrate etc.；With magnetic stirring apparatus at 30~80 DEG C
2~5h of lower stirring is in order that the molysite added is completely dissolved, to prevent from impacting loading process, for loading system
The quality of platanus fruit wool fibre is 0.5~2g；
3rd, platanus fruit wool fibre loads the acquisition and drying of ferriferrous oxide composite material：Treat the reactor in step 2
Room temperature is naturally cooled to, pyroreaction kettle is taken out, content is separated with magnet or removal after 3~8min is centrifuged in centrifuge
Supernatant, sediment is cleaned three times with absolute ethyl alcohol and distilled water respectively, and obtained sediment finally is placed in into vacuum drying chamber
In in 40~80 DEG C of vacuum dryings, drying time is 4~12h, produces dry platanus fruit wool fibre load ferroso-ferric oxide
Catalyst composite hollow tubular material；
Above-mentioned centrifuge speed is 3~8min of centrifugation under 2500~3500r/min.
Using ESEM (SEM), power spectrum determines (EDS), X-ray diffraction (XRD), infrared spectrum (FT-IR) and magnetic hysteresis
Curve is studied platanus fruit wool fibre load ferroso-ferric oxide Fenton catalyst, is as a result confirmed under these conditions
The material being made is the fiber-loaded ferriferrous oxide composite material of plant hollow.
Embodiment 1：
Weigh platanus fruit wool fibre and detergent and add the ratio of 5L ethanol in appearance in every 100g platanus fruits wool fibre
Mixed, be sufficiently stirred at room temperature with magnetic stirring apparatus after 30min in device, liquid is filtered off in vavuum pump, repeat this operation
Three times, obtain refined platanus fruit wool fibre；
0.5g ferric trichloride solids are weighed in container, 5ml hydrazine hydrates are added, 3h is stirred at 50 DEG C with magnetic stirring apparatus
It is completely dissolved and is added 0.1g and refine platanus fruit wool fibre, 2ml formaldehyde is added after being sufficiently stirred for is well mixed it.Will
Said mixture is added in 50ml pyroreaction kettles, and 4h is reacted in 130 DEG C of baking oven.Question response kettle naturally cools to room temperature,
Pyroreaction kettle is taken out, content supernatant is removed into centrifuge after 3000r/min centrifuges 5min, sediment uses nothing respectively
Water-ethanol and distilled water are cleaned three times, and finally obtained sediment is placed in vacuum drying chamber in 60 DEG C of vacuum dryings, dried
Time is 4h, produces the fiber-loaded ferroso-ferric oxide Fenton catalyst materials of dry hollow tubular plant hollow.
Embodiment 2：
Weigh platanus fruit wool fibre and detergent and add the ratio of 5L ethanol in appearance in every 100g platanus fruits wool fibre
Mixed, be sufficiently stirred at room temperature with magnetic stirring apparatus after 30min in device, liquid is filtered off in vavuum pump, repeat this operation
Three times, obtain refined platanus fruit wool fibre；
1g ferric sulfate solids are weighed in container, 5ml hydrazine hydrates are added, stirring 3h at 40 DEG C with magnetic stirring apparatus makes it
It is completely dissolved and adds 0.1g and refine platanus fruit wool fibre, 2ml formaldehyde is added after being sufficiently stirred for is well mixed it.Will be above-mentioned
Solution is added in 50ml pyroreaction kettles, and 6h is reacted in 110 DEG C of baking oven.Question response kettle naturally cools to room temperature, takes out high
Warm reactor, removes supernatant, sediment uses absolute ethyl alcohol respectively in centrifuge by content after 3000r/min centrifuges 5min
Clean three times, obtained sediment is placed in vacuum drying chamber in 50 DEG C of vacuum dryings with distilled water finally, drying time is
6h, produces the fiber-loaded ferroso-ferric oxide Fenton catalyst materials of dry hollow tubular plant hollow.
Embodiment 3：
Weigh platanus fruit wool fibre and detergent and add the ratio of 5L ethanol in appearance in every 100g platanus fruits wool fibre
Mixed, be sufficiently stirred at room temperature with magnetic stirring apparatus after 30min in device, liquid is filtered off in vavuum pump, repeat this operation
Three times, obtain refined platanus fruit wool fibre；
1g ferric trichloride solids are weighed in container, 5ml hydrazine hydrates are added, stirring 3h at 50 DEG C with magnetic stirring apparatus makes
It, which is completely dissolved and adds 0.1g, refines platanus fruit wool fibre, and 2ml formaldehyde is added after being sufficiently stirred for is well mixed it.Will be upper
State solution to add in 50ml pyroreaction kettles, 5h is reacted in 120 DEG C of baking oven.Question response kettle naturally cools to room temperature, takes out
Pyroreaction kettle, removes supernatant, sediment uses anhydrous second respectively in centrifuge by content after 3000r/min centrifuges 5min
Alcohol and distilled water are cleaned three times, and finally obtained sediment is placed in vacuum drying chamber in 60 DEG C of vacuum dryings, drying time
For 8h, the fiber-loaded ferroso-ferric oxide Fenton catalyst materials of dry hollow tubular plant hollow are produced.
Embodiment 4：
Weigh platanus fruit wool fibre and detergent and add the ratio of 5L ethanol in appearance in every 100g platanus fruits wool fibre
Mixed, be sufficiently stirred at room temperature with magnetic stirring apparatus after 30min in device, liquid is filtered off in vavuum pump, repeat this operation
Three times, obtain refined platanus fruit wool fibre.
1.2g ferric trichloride solids are weighed in container, 5ml hydrazine hydrates are added, 4h is stirred at 50 DEG C with magnetic stirring apparatus
It is completely dissolved and is added 0.1g and refine platanus fruit wool fibre, 2ml formaldehyde is added after being sufficiently stirred for is well mixed it.Will
Above-mentioned solution is added in 50ml pyroreaction kettles, and 5h is reacted in 120 DEG C of baking oven.Question response kettle naturally cools to room temperature, takes
Go out pyroreaction kettle, content is removed into supernatant in centrifuge after 3000r/min centrifuges 5min, sediment is respectively with anhydrous
Ethanol and distilled water are cleaned three times, finally obtained sediment are placed in vacuum drying chamber in 60 DEG C of vacuum dryings, when drying
Between be 6h, produce the fiber-loaded ferroso-ferric oxide Fenton catalyst materials of dry hollow tubular plant hollow.
The fiber-loaded ferroso-ferric oxide Fenton catalyst materials of plant hollow that the present embodiment is prepared, through applicant
It is demonstrated experimentally that can be used in the Fenton catalytic degradations of methylene blue dye wastewater, specific experiment step is as follows：
Fenton-like catalytic performance test：In 20P-250 types constant temperature oscillator (the upper grand experimental facilities Co., Ltd of Nereid)
It is middle to carry out, accurately measure and weigh the fiber-loaded ferroso-ferric oxide type Fenton catalyst sample of 20mg plant hollows, be added to dress
Have in the 50ml 250ml conical flasks of 10mg/ml methylene blue solutions, first the lucifuge and with 100r/min speed in oscillator
Reciprocal concussion 120min, reaches after adsorption equilibrium, 1.8ml hydrogenperoxide steam generators is added into 250ml conical flasks with pipette,
Shake in case with 100r/min speed continuation lucifuge concussion, took 4ml supernatants every 5~15 minutes, carried out in 3500r/min
5min is centrifuged, supernatant is taken.It is purple using 752N types by supernatant at the maximum absorption wavelength λ max=664nm of methylene blue
Outer visible spectrophotometer (upper Nereid section) determination sample absorbance, and logical formula D=[(A0-Ai)/A0] × 100% is calculated
Fenton catalysis degradation modulus, wherein A0To reach the absorbance of methylene blue solution during adsorption equilibrium, AiDetermined for timing sampling
The absorbance of methylene blue solution.
X-ray scanning, electron-microscope scanning, power spectrum, infrared spectrum and magnetic hysteresis are carried out to catalyst manufactured in the present embodiment bent
The measure of line, is as a result shown in Fig. 1~5：
Fig. 1 is the scanning electron microscope (SEM) photograph of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow, from profile angle
It is in micron tubular pattern to illustrate prepared material, and external diameter is about 25~30 μm, about 2~5 μm of ferroso-ferric oxide load layer thickness,
Internal diameter is about 20~28 μm, and inside has very big cavity area, and the material surface is coarse, is about the four of 35~60nm by particle diameter
Fe 3 O nano particle is constituted, and a is the overall pattern of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow；B is
The individual figure of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow；C is fiber-loaded four oxidation three of plant hollow
Iron type Fenton catalyst partial enlarged drawing；D is the structure of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow
Fracture enlarged drawing；
Fig. 2 is the power spectrum measure figure of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow, and table 1 represents each member
The percentage composition of element, explanation prepares products therefrom by carbon, iron, and the chemical element composition such as oxygen, these elements exactly plant hollow is fine
The basic element composition of dimension load ferroso-ferric oxide type Fenton catalyst composite；
Table 1
Fig. 3 is the X-ray diffractogram of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow, from crystalline structure
Angle illustrate that prepared product is plant hollow fiber and Fe3O4Composite；
Fig. 4 is the infrared spectrogram of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow, and it is from functional group
Constituting angle analysis, it is constituted.Infrared spectrum is mutually echoed with X-ray result, illustrates the outstanding bell seen in scanning electron microscope (SEM) photograph
The particulate matter of wooden fruit wool fibre surface attachment is Fe3O4Crystal grain, this also further illustrates Fe3O4Plane tree is successfully carried on
Fruit wool fibre surface, and it is that plant hollow fibrous outer is Fe that prepared product, which is internal layer,3O4Hollow tubular structures；
Fig. 5 is the hysteresis graph of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow, shows the present invention
Prepared platanus fruit wool fibre loads ferroso-ferric oxide type Fenton catalyst due to area load Fe3O4And possess certain
Magnetic, is very beneficial for the separation of post catalyst reaction.
In addition, with reference to Fig. 6~Fig. 7, it is known that the fiber-loaded ferroso-ferric oxide class of plant hollow manufactured in the present embodiment
Fenton catalyst is excellent to the degradation effect of methylene blue dye wastewater.Degradation rate reached in 120min 85% with
On, more than 95% is reached during 150min；Illustrate that platanus fruit wool fibre loads ferroso-ferric oxide type Fenton catalyst in methylene
Excellent Fenton catalytic degradation performances are shown in the degraded of base indigo plant dye wastewater；Fig. 6 is that plant hollow is fiber-loaded
Ferroso-ferric oxide type Fenton catalyst is to the Fenton catalytic degradation figures of methylene blue stimulated dye wastewater, and 1,2,3,4 is 60,
Platanus fruit wool fibre loads ferroso-ferric oxide type Fenton catalyst to the blue solution degradation crest of subunit when 90,120,30min,
Its absorbance that changes with time is significantly reduced, and illustrates that platanus fruit wool fibre loads ferroso-ferric oxide type Fenton catalyst pair
Subunit indigo plant solution degradation excellent effect；Fig. 7 is the repetition profit of the fiber-loaded ferroso-ferric oxide type Fenton catalyst of plant hollow
With figure, illustrate after by being used repeatedly, platanus fruit wool fibre load ferroso-ferric oxide type Fenton catalyst pair
Subunit indigo plant solution can still keep good degradation effect.
Embodiment 5：
Weigh platanus fruit wool fibre and detergent and add the ratio of 5L ethanol in appearance in every 100g platanus fruits wool fibre
Mixed, be sufficiently stirred at room temperature with magnetic stirring apparatus after 30min in device, liquid is filtered off in vavuum pump, repeat this operation
Three times, obtain refined platanus fruit wool fibre；
1g ferric nitrate solids are weighed in container, 5ml hydrazine hydrates are added, stirring 2h at 70 DEG C with magnetic stirring apparatus makes it
It is completely dissolved and adds 0.1g and refine platanus fruit wool fibre, 2ml formaldehyde is added after being sufficiently stirred for is well mixed it.Will be above-mentioned
Solution is added in 50ml pyroreaction kettles, and 3h is reacted in 140 DEG C of baking oven.Question response kettle naturally cools to room temperature, takes out high
Warm reactor, removes supernatant, sediment uses absolute ethyl alcohol respectively in centrifuge by content after 3000r/min centrifuges 5min
Clean three times, obtained sediment is placed in vacuum drying chamber in 50 DEG C of vacuum dryings with distilled water finally, drying time is
6h, produces the fiber-loaded ferroso-ferric oxide Fenton catalyst materials of dry hollow tubular plant hollow.
Embodiment 6：
Weigh platanus fruit wool fibre and detergent and add the ratio of 5L ethanol in appearance in every 100g platanus fruits wool fibre
Mixed, be sufficiently stirred at room temperature with magnetic stirring apparatus after 30min in device, liquid is filtered off in vavuum pump, repeat this operation
Three times, obtain refined platanus fruit wool fibre；
1.5g ferric trichloride solids are weighed in container, 5ml hydrazine hydrates are added, 2h is stirred at 70 DEG C with magnetic stirring apparatus
It is completely dissolved and is added 0.1g and refine platanus fruit wool fibre, 2ml formaldehyde is added after being sufficiently stirred for is well mixed it.Will
Above-mentioned solution is added in 50ml pyroreaction kettles, and 3h is reacted in 130 DEG C of baking oven.Question response kettle naturally cools to room temperature, takes
Go out pyroreaction kettle, 3000r/min is centrifuged and supernatant is removed after 5min in centrifuge, sediment uses absolute ethyl alcohol and steaming respectively
Distilled water is cleaned three times, finally obtained sediment is placed in vacuum drying chamber in 40 DEG C of vacuum dryings, drying time is 8h, i.e.,
The fiber-loaded ferroso-ferric oxide Fenton catalyst materials of hollow tubular plant hollow that must be dried.
Claims (5)
1. a kind of fiber-loaded type Fenton catalyst of plant hollow, it is characterised in that including carrier and be carried on carrier
Catalyst；
Described carrier is plant hollow fiber, and described catalyst is heterogeneous type Fenton catalyst；
Described plant hollow fiber is platanus fruit wool fibre, and the external diameter of platanus fruit wool fibre is 25~30 μm, plane tree
The internal diameter of fruit wool fibre is 20~28 μm；
Described heterogeneous type Fenton catalyst is ferroso-ferric oxide；
Described is carried on supported catalyst thickness for 2~5 μm.
2. the fiber-loaded type Fenton catalyst of plant hollow as claimed in claim 1, it is characterised in that four described oxygen
Change three-iron is ferroferric oxide nano granules, and the particle diameter of ferroferric oxide nano granules is 35~60nm.
3. preparing the method for the fiber-loaded type Fenton catalyst of plant hollow described in claim 1 or 2, its feature exists
In, including will be sunk after the plant hollow fiber after trivalent iron salt, reducing agent, cleaning and stabilizer mixing by hydro-thermal reaction
Starch, then sediment is cleaned and dried obtains the fiber-loaded type Fenton catalyst of plant hollow；
Described trivalent iron salt and the use magnitude relation of reducing agent are that 0.1~2g trivalent iron salts add 5ml reducing agents, described trivalent
Molysite is that 5~20g trivalent iron salts add the platanus fruit after 1g is cleaned with magnitude relation with the platanus fruit wool fibre after cleaning
Wool fibre, described trivalent iron salt and the use magnitude relation of stabilizer add 1~5ml stabilizer for 0.1~2g trivalent iron salt；
Described trivalent iron salt is ferric trichloride, ferric sulfate or ferric nitrate, and described reducing agent is hydrazine hydrate, described stabilization
Agent is formaldehyde.
4. the method as claimed in claim 3 for preparing the fiber-loaded type Fenton catalyst of plant hollow, it is characterised in that
Described hydrothermal reaction condition is that 2~8h is reacted under 110~150 DEG C of temperature conditionss.
5. the method as claimed in claim 3 for preparing the fiber-loaded type Fenton catalyst of plant hollow, it is characterised in that
Described drying condition is 40~80 DEG C of 4~12h of vacuum drying.
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| CN105347461A (en) * | 2015-11-30 | 2016-02-24 | 无锡工源机械有限公司 | Heterogeneous fenton catalysis filler |
| CN106830092B (en) * | 2017-01-23 | 2019-03-08 | 重庆市畜牧科学院 | It is a kind of with the iron molybdate/iron tungstate preparation method and product of 1-dimention nano fibre structure and application |
| CN106902822A (en) * | 2017-03-02 | 2017-06-30 | 河北科技大学 | A kind of hollow ferroso-ferric oxide core-shell structure nano particle of Silica-coated and preparation method thereof |
| CN107245771B (en) * | 2017-06-29 | 2019-09-13 | 天津工业大学 | A kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst |
| CN107570213A (en) * | 2017-10-12 | 2018-01-12 | 湖北工业大学 | A kind of preparation method of ferroso-ferric oxide paper substrate heterogeneous catalysis material |
| CN109987692B (en) * | 2019-04-02 | 2021-10-22 | 温州医科大学 | Method for enhancing treatment of organic wastewater by Fenton-like system constructed based on glyoxylic acid |
| CN110433871A (en) * | 2019-08-09 | 2019-11-12 | 宜兴国际环保城科技发展有限公司 | A kind of disintegration-type tubular type free-radical oxidation method for preparing catalyst |
| CN115532312A (en) * | 2022-10-10 | 2022-12-30 | 中国民航大学 | Preparation method of biomass cellulose composite magnetic iron oxide nano catalyst |
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