CN107570170A - A kind of ferroso-ferric oxide and manganese dioxide complex class fenton catalyst and preparation method thereof - Google Patents
A kind of ferroso-ferric oxide and manganese dioxide complex class fenton catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of ferroso-ferric oxide and manganese dioxide complex class fenton catalyst.The catalyst includes diatomite, and the mass ratio of diatomite and ferroso-ferric oxide is 1:0.3~1:0.6, the mass ratio of diatomite and manganese dioxide is 1:1~1:2.Its preparation method is：Using natural diatomite as carrier, successively pass through the pyrolysis and hydro-thermal reaction in organic solvent medium, ferroferric oxide nano granules with high degree of dispersion and manganese dioxide nano-plates are carried on to the surface of natural diatomaceous earth successively, form natural tripolite loading nano ferroso-ferric oxide and manganese dioxide complex class fenton catalyst.Manganese dioxide, ferroso-ferric oxide and diatomite are mutually combined closely in the catalyst of the present invention, form special three-decker, and the catalyst is with good dispersion, adsorptivity are strong in water, catalytic activity is high, is easily recycled outstanding advantages of recycling.Preparation technology flow of the present invention is simple, easy to operate, low for equipment requirements, it is easy to accomplish industrialized production.
Description
Technical field
The invention belongs to environment-friendly function material, nano material and catalysis material preparing technical field, and in particular to Yi Zhongli
Nano ferriferrous oxide and manganese dioxide NEW TYPE OF COMPOSITE class fenton catalyst and preparation method thereof are loaded with natural diatomaceous earth.
Background technology
Fenton technology（Fenton）It is the important method of degradation of organic waste water in industrial production, it utilizes ferrous ion（Fe2 +）Catalyst and hydrogen peroxide（H2O2）Effect, produce the hydroxyl radical free radical with strong oxidizing property（·OH）Organic pollution is complete
Mineralizing and degrading, there is few equipment investment, efficiency high, the simple distinguishing feature of operating procedure.However, Fenton technology is needed relatively low
PH environment in carry out（pH=3~4）, while also exist easily produce the accessory substances such as a large amount of red muds, catalyst can not recycle,
The problems such as hydrogen peroxide stores and cost of transportation is high, limits it and is widely applied.
Compared to traditional Fenton catalysis process, based on potentiometric titrations（·SO4 -）Heterogeneous Fenton technology just by
To more and more extensive concern and attention, there is wide work pH scopes, no coupling product, efficiency high and medicament transport convenient storage
Many advantages, such as, while traditional Fenton catalysis shortcoming is effectively overcome, also with stronger catalytic performance, there is wide answer
Use prospect.
It is with metal oxide in such heterogeneous catalysis technology（Cerium oxide, cobalt oxide, manganese dioxide, cupric oxide
Deng）For catalyst, persulfate or hydrogen peroxymonosulfate salt oxidizing agent are catalyzed, produces the potentiometric titrations with strong oxidizing property
（·SO4 -）Pollutant is degradable.Among numerous catalyst, manganese dioxide（MnO2）With ferroso-ferric oxide（Fe3O4）Cause
It has wide material sources, nontoxic and cheap significant advantage, it has also become has really application in actual waste water process field
The catalyst of value.For manganese dioxide, although it has higher catalytic activity, in the application process of reality,
Need to be reclaimed using the filtering or centrifugal method that are costly and inefficient.And for ferroso-ferric oxide（Fe3O4）, it is catalyzed
It is active then to be less than manganese dioxide, but its intrinsic magnetic so as in the application process of reality by efficiency high, into
This low magnetic selection method carries out recycling.In addition, easily aggregation for both catalyst also all be present with disperseing in water
Property difference the problem of, especially ferroferric oxide nano granules easily formed soft aggregate even hard agglomeration, it is difficult in water disperse,
As its wide variety of another bottleneck.
In view of the shortcomings of the prior art, it is necessary to research and develop new composite, the property of different component has been given play to greatest extent
Can, the maximization of catalytic performance is realized, the defects of to overcome the limitation of prior art and exist, and further improving performance,
Obtain bigger application value.
The content of the invention
It is an object of the invention to overcome prior art defect, use is cheap, wide material sources, environment-friendly, duct
The natural diatomaceous earth abundant, absorption property is excellent is used as carrier, the method that use is simple to operate, efficiency high, cost are low, successively general
Ferroferric oxide nano granules with high degree of dispersion structure are carried on its surface with manganese dioxide nano-plates catalyst, form tool
There is the NEW TYPE OF COMPOSITE class fenton catalyst that adsorptivity is strong, catalytic activity is high and is easily recycled, obtain bigger application valency
Value.
A kind of complex class fenton catalyst of ferroso-ferric oxide and manganese dioxide, the catalyst include diatomite, silicon
The mass ratio of diatomaceous earth and ferroso-ferric oxide is 1:0.3~1:0.6, the mass ratio of diatomite and manganese dioxide is 1:1~1:2.Four oxygen
Change three-iron, manganese dioxide and diatomite form composite, using respective advantage, it is effectively perfect reunite asked with dispersed
Topic, realizes the reinforcing of catalytic performance.The composite has magnetic, is reclaimed using magnetic selection method, simultaneously because titanium dioxide
The combination of manganese and ferroso-ferric oxide can produce concerted catalysis effect in catalytic reaction process, its catalytic activity is far above
Single manganese dioxide or ferroso-ferric oxide.
It is discoid under ESEM and surface distributed loose structure preferably, the diatomite is natural diatomaceous earth,
Described discoid a diameter of 20 ~ 50 μm.Natural diatomite is a kind of natural porous mineral, and main component is unformed two
Silica, be widely used in numerous areas or even food service industrys such as environmental protection, filterings, have stability height, aboundresources,
The features such as inexpensive and nontoxic, especially also have that adsorptivity is strong, outstanding properties of the good dispersion in water.
Preferably, the ferroso-ferric oxide is nanoscale, its a diameter of 5 ~ 10nm, the manganese dioxide is nanoscale,
Its a diameter of 30 ~ 50nm.The active surface that nano-scale particle exposes is more, and catalytic effect is more preferably.
Invention further provides a kind of side for the complex class fenton catalyst for preparing ferroso-ferric oxide and manganese dioxide
Method, comprise the following steps：
（1）Diatomite and ferric acetyl acetonade are fully dispersed in organic solvent by way of mechanical strong mixing, until being formed
Uniform primary suspension；
（2）The primary suspension is heated to certain temperature with certain heating rate under inert gas shielding, waits to be incubated
Room temperature is naturally cooled to after certain time, suspension is subjected to separation of solid and liquid, after obtained product is washed with water several times, is obtained black
Color solid product；
（3）The black solid product and potassium permanganate are dispersed in water by mechanical strong mixing mode, formed uniform time
Level suspension；
（4）The secondary suspension is put into autoclave and carries out hydro-thermal reaction, natural cooling after question response certain time
To room temperature, the suspension after hydro-thermal reaction is subjected to separation of solid and liquid, obtained solid product is washed with water to be dried to perseverance afterwards several times
Weight, obtain the class Fenton composite catalyst of final natural diatomaceous earth load nano ferriferrous oxide and manganese dioxide.
Preferably, step（1）The mass ratio of middle diatomite and ferric acetyl acetonade is 1:1.2~1:2.5, it is described organic molten
Agent is any one in triethylene glycol, glycerine, sulfolane, octadecylene.
Preferably, step（2）Described in inert atmosphere be nitrogen, any one in argon gas.
As further preferred, step（2）Described in heating rate be 2 DEG C/min ~ 5 DEG C/min, heating-up temperature is 250 DEG C
~ 280 DEG C, soaking time is the min of 30 min ~ 60.
Further, step（3）Middle potassium permanganate and step（1）Described in diatomaceous weight ratio be 1.82:1~3.64:
1。
Preferably, step（3）Described in the solids content of secondary suspension be 15g/L ~ 30g/L.
Preferably, step（4）The temperature of middle hydro-thermal reaction is 120 DEG C ~ 160 DEG C, time of hydro-thermal reaction for 6 hours ~
12 hours.
Compared with prior art, remarkable advantage of the invention is with having the beneficial effect that：
（1）The catalyst carrier used in the present invention is natural diatomaceous earth, and its main component is unformed silica, such
Natural minerals have extensive utilization in wastewater treatment and food processing field, therefore have fabulous environment friendly, simultaneously
Also there is preferable heat endurance and chemical stability；In addition, the catalysis material in composite catalyst is ferroso-ferric oxide and dioxy
Change manganese, its environment friendly is much better than other metal oxide catalysts（Such as cupric oxide, cobaltosic oxide, cerium oxide）, because
This composite has fabulous security in practical application, does not produce secondary pollution.（2）The composite catalyst of the present invention,
It is carrier to rely on natural diatomaceous earth mineral, covers the ferriferrous oxide nano with individual layer and high degree of dispersion successively on its surface
Grain and manganese dioxide nano-plates, the double-decker of uniqueness is formed, reunited in raising nano-catalyst particles dispersiveness, suppression same
When, the contact between ferroferric oxide nano granules and manganese dioxide nano-plates both nanocatalysts is substantially increased, can
Concerted catalysis acts between both efficient hardenings, realizes being substantially improved for catalytic performance.Meanwhile by manganese dioxide nano-plates and four oxygen
Change three iron nano-particles to be fixed on the diatomaceous surface of micron-scale, be greatly improved its recuperability, effectively prevent
The loss of actual application, realize and excellent recycle performance.（3）The present invention by natural diatomaceous earth, ferroso-ferric oxide with
Manganese dioxide is formed, and forms multilayer coating structure, and penetralia is diatomite, serves as the supporter of whole composite, is relied on
It has the surface of strongly hydrophilic, dispersive property of the enhancing composite in water, while its excellent absorption property can also be inhaled
It is attached and be enriched with pollutant, improve the catalytic effect of catalyst；Intermediate layer is ferroferric oxide nano granules, and its intrinsic magnetic makes
Recovery cycling and reutilization can be carried out using magnetic selection method by obtaining composite, while be used as catalyst, it may have preferably catalysis
Performance, organic pollution is decomposed；Outermost layer is manganese dioxide nano-plates, itself has a stronger catalytic performance, while with
The ferroso-ferric oxide synergy of internal layer, the two promotes Mn by the electron transmission in catalytic process4+/Mn3+With Fe3+/Fe2+Oxygen
Change the progress of reduction reaction, greatly improve the generation speed of potentiometric titrations, realize effective lifting of catalytic degradation speed.Cause
This, based on the performance between different component and mutual synergy so that composite catalyst shows excellent urge
Change performance and operational.（4）The preparation technology of the composite of the present invention is simple, and easy to operate, used raw material is only day
Right three kinds of diatomite, ferric acetyl acetonade and potassium permanganate, are the common and cheap raw material of industry.Loaded in ferroso-ferric oxide
Cheng Zhong, used organic solvent are merely possible to reaction medium, and itself does not participate in reaction, repeatable to recycle；In dioxy
Change manganese loading process, only using water as reaction medium, can also be reused.Course of reaction only needs to control reaction temperature one
Fixed scope, without accurate temperature control.
Composite catalyst obtained by the present invention is by diatomite, ferroferric oxide nano granules and manganese dioxide nano
Piece is formed, and generally shows clad structure, and its specific surface area can reach 200 m2/ more than g, there is pole to organic pollution
Good absorption and degradation property, while it is easily scattered in water, and effectively recovery can be carried out again by the magnetic selection method of simplicity
Utilize.Therefore, the composite catalyst obtained by method provided by the invention can be widely applied to the class Fenton catalysis of organic wastewater
Degraded field.
The preparation method of composite catalyst provided by the invention is simple, and the technological process of production is simple, simple to operate, excessively program control
System is easy, raw material is cheap and easy to get, it is easy to accomplish the industrial production of scale.
Brief description of the drawings
Fig. 1：Natural diatomaceous earth loads ferroso-ferric oxide and the X-ray diffractogram of manganese dioxide complex class fenton catalyst
Spectrum；
Fig. 2：The scanning electron microscope (SEM) photograph of natural diatomaceous earth；
Fig. 3：Natural diatomaceous earth loads ferroso-ferric oxide and the scanning electron microscope (SEM) photograph of manganese dioxide complex class fenton catalyst；
Fig. 4：Natural diatomaceous earth loads ferroso-ferric oxide and the energy spectrum diagram of manganese dioxide complex class fenton catalyst；
Fig. 5：Natural diatomaceous earth loads ferroso-ferric oxide and the hysteresis curve figure of manganese dioxide complex class fenton catalyst；
Fig. 6：Natural diatomaceous earth loads ferroso-ferric oxide and the dispersiveness and magnetic recyclability of manganese dioxide complex class fenton catalyst
Energy.
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.It should be appreciated that specific embodiment described herein is only used for explaining this hair
It is bright, the features and advantages of the present invention are further shown, and be not intended to limit the present invention.
Embodiment 1
10g natural diatomaceous earth is weighed, it is being fully dispersed in 0.60L triethylene glycol under conditions of being stirred vigorously, is formed
Uniform suspension.The ferric acetyl acetonade for weighing 20.00g is added in above-mentioned suspension, and is stirred continuously until its is complete
Dissolving, obtains primary suspension.Above-mentioned primary suspension is heated to 3 DEG C/min heating rate under nitrogen protection
250 DEG C, and it is incubated 30min.After question response terminates, room temperature is naturally cooled to.Reacted solid-liquid suspension is separated, obtained
To solid product be washed with water 3 times.Solid product after washing and 18.2g potassium permanganate are added under conditions of stirring
In 0.50L water, and 10min is stirred continuously, obtains secondary suspension.The secondary suspension is moved into autoclave, risen
Warm to 150 DEG C are reacted 6 hours.Question response naturally cools to room temperature after terminating, and the solid-liquid suspension in reactor is separated, separation
Solid product afterwards is washed with water three times, with the temperature drying not higher than 80 DEG C to constant weight in vacuum drying chamber, so as to obtain
Final tripolite loading nano ferroso-ferric oxide and manganese dioxide complex class fenton catalyst.The X ray of composite catalyst spreads out
Penetrate（XRD）Analysis result is shown in Fig. 1, and the stereoscan photograph of natural diatomaceous earth is shown in Fig. 2, and the scanning electron microscopic picture of composite catalyst is shown in
Fig. 3, the energy spectrum diagram of composite catalyst are shown in Fig. 4, and the hysteresis curve figure of composite catalyst is shown in Fig. 5, the dispersiveness and magnetic of composite
Recyclability is shown in Fig. 6.Analysis result shows, is the characteristics of the material：Natural diatomite presentation is discoid, and surface distributed has rich
Rich duct, discoid diatomaceous a diameter of 20 ~ 50 μm, a diameter of 5 ~ 10nm of ferroso-ferric oxide, the diameter of manganese dioxide
For 30 ~ 50nm；In the composite, ferroferric oxide nano granules in a highly dispersed state and manganese dioxide uniform load in
Diatomaceous surface, the disk loose structure of natural diatomaceous earth are completely retained；Nanometer is presented in outermost manganese dioxide
Sheet, bigger surface can be shown, form abundant pore structure so that composite obtain more excellent absorption property with
Catalytic performance.
Embodiment 2
10g natural diatomaceous earth is weighed, it is being fully dispersed in 0.80L octadecylene under conditions of being stirred vigorously, is formed
Uniform suspension.The ferric acetyl acetonade for weighing 14.00g is added in above-mentioned suspension, and is stirred continuously until its is complete
Dissolving, obtains primary suspension.The primary suspension is heated to 270 under argon gas protection with 4 DEG C/min heating rate
DEG C, and it is incubated 40min.After question response terminates, room temperature is naturally cooled to.Reacted solid-liquid suspension is separated, obtained
Solid product be washed with water 3 times.Solid product after washing and 22g potassium permanganate are added into 0.60L under conditions of stirring
In water, and 10min is stirred continuously, obtains secondary suspension.The secondary suspension is moved into autoclave, is warming up to
120 DEG C are reacted 8 hours.Question response naturally cools to room temperature after terminating, and the solid-liquid suspension in reactor is separated, after separation
Solid product is washed with water three times, final so as to obtain with the temperature drying not higher than 80 DEG C to constant weight in vacuum drying chamber
Tripolite loading nano ferroso-ferric oxide and manganese dioxide complex class fenton catalyst.
Embodiment 3
10g natural diatomaceous earth is weighed, it is being fully dispersed in 1L glycerine under conditions of being stirred vigorously, is formed uniform
Suspension.The ferric acetyl acetonade for weighing 21.00g is added in above-mentioned suspension, and be stirred continuously until its be completely dissolved, obtain
To primary suspension.The primary suspension is heated to 265 DEG C with 5 DEG C/min heating rate under argon gas protection, and protected
Warm 35min.After question response terminates, room temperature is naturally cooled to.Reacted solid-liquid suspension is separated, obtained solid production
Thing is washed with water 3 times.Solid product after washing and 28g potassium permanganate are added in 0.5L water under conditions of stirring, not
Disconnected stirring 10min, obtains secondary suspension.The secondary suspension is moved into autoclave, is warming up to 160 DEG C of reactions 6
Hour.Question response naturally cools to room temperature after terminating, and the solid-liquid suspension in reactor is separated, and the solid product after separation is used
Water washing three times, with the temperature drying not higher than 80 DEG C to constant weight in vacuum drying chamber, so as to which the diatomite for obtaining final is born
Carry nano ferriferrous oxide and manganese dioxide complex class fenton catalyst.
Embodiment 4
10g natural diatomaceous earth is weighed, it is being fully dispersed in 0.5L sulfolane under conditions of being stirred vigorously, is formed equal
Even suspension.The ferric acetyl acetonade for weighing 25.00g is added in above-mentioned suspension, and is stirred continuously until it is completely molten
Solution, obtains primary suspension.The primary suspension is heated to 280 DEG C with 2 DEG C/min heating rate under nitrogen protection,
And it is incubated 60 min.After question response terminates, room temperature is naturally cooled to.Reacted solid-liquid suspension is separated, obtained
Solid product is washed with water 3 times.Solid product after washing and 36.4g potassium permanganate are added into 0.6L water under conditions of stirring
In, and 10min is stirred continuously, obtain secondary suspension.The secondary suspension is moved into autoclave, is warming up to 160
DEG C reaction 12 hours.Question response naturally cools to room temperature after terminating, and the solid-liquid suspension in reactor is separated, consolidating after separation
Body product is washed with water three times, final so as to obtain with the temperature drying not higher than 80 DEG C to constant weight in vacuum drying chamber
Tripolite loading nano ferroso-ferric oxide and manganese dioxide complex class fenton catalyst.
Testing result of the table one for embodiment products obtained therefrom and the degradation effect to organic pollution.（Note：Catalytic process is anti-
Temperature control is answered at 25 ± 1 DEG C, using potassium hydrogen persulfate as oxidant, dosage 10mmol/L；Use Congo red, tetrachlorobenzene
Goal response thing of the machine pollution as degraded is common are in the industry such as phenol, phenol, bisphenol-A, its initial concentration is 20mg/L；
Tripolite loading nano ferroso-ferric oxide and concentration of the manganese dioxide complex class fenton catalyst in reaction solution are 0.1g/L,
Reaction time is 60min）.
Table one
Tripolite loading nano ferroso-ferric oxide and manganese dioxide complex class fenton catalyst are to organic pollution as shown in Table 1
Degradation rate it is very high, may be such that organic pollution is effectively degraded within the reaction time of 60 minutes, belong to efficient class
Fenton catalyst.
The general principle and principal character and advantages of the present invention of the present invention, the technology of the industry has been shown and described above
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention, the claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
- A kind of 1. complex class fenton catalyst of ferroso-ferric oxide and manganese dioxide, it is characterised in that：The catalyst includes The mass ratio of diatomite, diatomite and ferroso-ferric oxide is 1:0.3~1:0.6, the mass ratio of diatomite and manganese dioxide is 1:1~ 1:2。
- 2. catalyst according to claim 1, it is characterised in that：The diatomite is natural diatomaceous earth, under ESEM For discoid and surface distributed loose structure, described discoid a diameter of 20 ~ 50 μm.
- 3. catalyst according to claim 1, it is characterised in that：The ferroso-ferric oxide is nanoscale, its a diameter of 5 ~ 10nm, the manganese dioxide are nanoscale, its a diameter of 20 ~ 50nm.
- 4. a kind of preparation method for preparing any catalyst of claims 1 to 3, comprises the following steps：（1）Diatomite and ferric acetyl acetonade are fully dispersed in organic solvent by way of mechanical strong mixing, until being formed Uniform primary suspension；（2）The primary suspension is heated to certain temperature with certain heating rate under inert gas shielding, waits to be incubated Room temperature is naturally cooled to after certain time, suspension is subjected to separation of solid and liquid, after obtained product is washed with water several times, is obtained black Color solid product；（3）The black solid product and potassium permanganate are dispersed in water by mechanical strong mixing mode, formed uniform time Level suspension；（4）The secondary suspension is put into autoclave and carries out hydro-thermal reaction, natural cooling after question response certain time To room temperature, the suspension after hydro-thermal reaction is subjected to separation of solid and liquid, obtained solid product is washed with water to be dried to perseverance afterwards several times Weight, obtain the class Fenton composite catalyst of final natural diatomaceous earth load nano ferriferrous oxide and manganese dioxide.
- 5. according to the method for claim 4, step（1）The mass ratio of middle diatomite and ferric acetyl acetonade is 1:1.2~1: 2.5, the organic solvent is any one in triethylene glycol, glycerine, sulfolane, octadecylene.
- 6. according to the method for claim 4, step（2）Described in inert atmosphere be nitrogen, any one in argon gas.
- 7. according to the method for claim 4, step（2）Described in heating rate be 2 DEG C/min ~ 5 DEG C/min, heating-up temperature For 250 DEG C ~ 280 DEG C, soaking time is 30min ~ 60min.
- 8. according to the method for claim 4, step（3）Middle potassium permanganate and step（1）Described in diatomaceous weight ratio For 1.82:1~3.64:1.
- 9. according to the method for claim 4, step（3）Described in the solids content of secondary suspension be 15g/L ~ 30g/L.
- 10. according to the method for claim 4, step（4）The temperature of middle hydro-thermal reaction is 120 DEG C ~ 160 DEG C, hydro-thermal reaction Time be 6 hours ~ 12 hours.
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| CN110156137A (en) * | 2019-04-29 | 2019-08-23 | 北京大学深圳研究生院 | The instant on-line processing method of organic wastewater |
| CN113426418A (en) * | 2021-06-16 | 2021-09-24 | 山东银鹰股份有限公司 | Nano-cellulose/nano-double transition metal oxide ternary composite material and preparation method and application thereof |
| CN113797890A (en) * | 2021-10-11 | 2021-12-17 | 吉林大学 | Method for preparing catalytic and adsorption material from deep sea clay |
| CN114534741A (en) * | 2022-01-21 | 2022-05-27 | 厦门理工学院 | Attapulgite/manganese dioxide/ferroferric oxide nano composite material and preparation method and application thereof |
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| CN116196926A (en) * | 2023-02-23 | 2023-06-02 | 合肥工业大学 | Cu (copper) alloy x+1 Fe 2 O 4 DE nanocomposite and preparation method and application thereof |
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| CN110156137A (en) * | 2019-04-29 | 2019-08-23 | 北京大学深圳研究生院 | The instant on-line processing method of organic wastewater |
| CN113426418A (en) * | 2021-06-16 | 2021-09-24 | 山东银鹰股份有限公司 | Nano-cellulose/nano-double transition metal oxide ternary composite material and preparation method and application thereof |
| CN113797890A (en) * | 2021-10-11 | 2021-12-17 | 吉林大学 | Method for preparing catalytic and adsorption material from deep sea clay |
| CN114534741A (en) * | 2022-01-21 | 2022-05-27 | 厦门理工学院 | Attapulgite/manganese dioxide/ferroferric oxide nano composite material and preparation method and application thereof |
| CN114534741B (en) * | 2022-01-21 | 2023-10-20 | 厦门理工学院 | Attapulgite/manganese dioxide/ferroferric oxide nanocomposite and preparation method and application thereof |
| CN115043540A (en) * | 2022-06-14 | 2022-09-13 | 沈阳理工大学 | Device and method for treating iron and steel hydrochloric acid pickling waste liquid by using flue gas, filtering type catalytic converter and application |
| CN115043540B (en) * | 2022-06-14 | 2024-01-23 | 沈阳理工大学 | Device for treating steel hydrochloric acid pickling waste liquid by utilizing flue gas, method thereof, filter-type catalyst and application |
| CN116196926A (en) * | 2023-02-23 | 2023-06-02 | 合肥工业大学 | Cu (copper) alloy x+1 Fe 2 O 4 DE nanocomposite and preparation method and application thereof |
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