CN108220824A - A kind of ferrum-based amorphous alloy strip and its application in dyeing and printing sewage degradation treatment - Google Patents
A kind of ferrum-based amorphous alloy strip and its application in dyeing and printing sewage degradation treatment Download PDFInfo
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- CN108220824A CN108220824A CN201711346001.1A CN201711346001A CN108220824A CN 108220824 A CN108220824 A CN 108220824A CN 201711346001 A CN201711346001 A CN 201711346001A CN 108220824 A CN108220824 A CN 108220824A
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- ferrum
- based amorphous
- amorphous alloy
- alloy strip
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/003—Making ferrous alloys making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
-
- 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
Abstract
The invention belongs to sewage treating material fields, disclose a kind of ferrum-based amorphous alloy strip and its application in dyeing and printing sewage degradation treatment.The Elements Atom percentage of the ferrum-based amorphous alloy strip forms：Fe：68%~78%, Co：0~10%, Si：8%~9%, B：12%~14%, Sm：0~4%, Gd：0~4%.The ferrum-based amorphous alloy strip preparation method of the present invention is simple, easily realizes volume production, by adding different alloying elements, can improve the speed of its sewage degradation, and amorphous ribbon can be recycled and is used for multiple times, and have the advantages that at low cost, wastewater treatment efficiency is notable.
Description
Technical field
The invention belongs to sewage treating material fields, and in particular to a kind of ferrum-based amorphous alloy strip and its in dyeing and printing sewage
Application in degradation treatment.
Background technology
Since 1875 for the first time by Perkin synthetic organic dyes since, until last century end, the annual output of organic dyestuff
Amount is close to 100 tons, and wherein more than half is azo dyes.Azo dyes is a kind of organic compound of azo group both ends connection aryl
Object is fabric clothing most widely used one kind synthetic dyestuffs in dyeing and printing process, for a variety of natural and synthetic fibers
Dyeing and stamp, are also used for the coloring of paint, plastics, rubber etc..According to investigation, the dyestuff for having about 12% every year flows into waste water
In, if waste water is not made to flow into rivers and lakes or underground water, ecological environment will be caused greatly by appropriate processing
Destruction.
The method of existing frequently-used processing azo dyes mainly active carbon adsorption, biological degradation method, photocatalytic method etc..
Active carbon adsorption is a kind of traditional processing method, but the molecule knot of azo dyes can not be destroyed by being only limitted to physical absorption
Structure, subsequent processing work are still sufficiently complex.Biodegradable rule is often limited to the environmental condition of degradation, needs comparable
Equipment guarantee improves cost, limits its use scope.Photocatalytic method since the price is very expensive, make its promote and apply by
Limitation is arrived.
Amorphous alloy material can be used for azo dyes of degrading, and relative to zeroth order iron powder, the drop of Fe-based amorphous alloy
Solution speed can improve 1000 times of (S.Xie, P.Huang, J.J.Kruzic, X.Zeng and H.Qian, Scientific
Reports, 2016,6,1~10), meanwhile, Fe-based amorphous alloy has ferromagnetism, and band can be recycled and is used for multiple times.Therefore,
Degradation sewage (non-illuminated conditions) of the Fe-based amorphous alloy for printing and dyeing is had a good application prospect, but it is to dyeing waste water
Degradation capability be still expected to further improve.
Invention content
In place of above shortcoming and defect of the existing technology, primary and foremost purpose of the invention is to provide a kind of iron-based
AMORPHOUS ALLOY RIBBONS.
Another object of the present invention is to provide the preparation method of above-mentioned ferrum-based amorphous alloy strip.
It is still another object of the present invention to provide above-mentioned ferrum-based amorphous alloy strip answering in dyeing and printing sewage degradation treatment
With.
The object of the invention is achieved through the following technical solutions：
A kind of ferrum-based amorphous alloy strip, the Elements Atom percentage composition of the ferrum-based amorphous alloy strip are：Fe：
68%~78%, Co：0~10%, Si：8%~9%, B：12%~14%, Sm：0~4%, Gd：0~4%.
Preferably, the Elements Atom percentage composition of the ferrum-based amorphous alloy strip is：Fe：68%~78%, Co：6
~10%, Si：8%~9%, B：12%~14%, Sm：0~4% or Fe：68%~78%, Si：8%~9%, B：12%
~14%, Gd：0~4%.
The specification limit of the ferrum-based amorphous alloy strip is：2~6mm of strip width, 20~100 μm of beam thickness, item
1~20mm of strip length.
The preparation method of above-mentioned ferrum-based amorphous alloy strip, including following preparation process：
(1) by Fe：68%~78%, Co：0~10%, Si：8%~9%, B：12%~14%, Sm：0~4%, Gd：0
~4% element percentage carries out dispensing, and raw metal is carried out surface preparation；
(2) it is the melting in vacuum melting furnace of step (1) pretreated raw metal is uniform, obtain alloy mother's ingot；
(3) it by after alloy mother ingot progress surface preparation obtained by step (2), carries out getting rid of band by getting rid of band machine, obtain described
Ferrum-based amorphous alloy strip.
Preferably, the linear resonance surface velocity that band is got rid of described in step (3) is 30~50m/s.
Preferably, the surface preparation described in step (1) and step (3) refers to carry out surface scale disengaging.
Preferably, the ferrum-based amorphous alloy strip has full amorphous state or the multiple structural features of amorphous state+α-Fe.
Application of the above-mentioned ferrum-based amorphous alloy strip in dyeing and printing sewage degradation treatment.
Preferably, in the application process, 20~1000mg/L of concentration of dyestuff, Fe-based amorphous alloy item in dyeing and printing sewage
The addition of band is 0.1~100g/L.
Preferably, in the application process, the temperature control of processing is room temperature~100 DEG C, and mechanical agitation is 0~1000r/
min。
Gained ferrum-based amorphous alloy strip of the invention has the following advantages that and advantageous effect：
The ferrum-based amorphous alloy strip preparation method of the present invention is simple, easily realizes volume production, by adding different alloy members
Element can improve the speed of its sewage degradation, further improve its degradation capability to dyeing waste water；And amorphous ribbon can follow
Ring is used for multiple times, and the dyestuff removal rate of 60 minutes after continuous degradation 5 times has at low cost, sewage disposal up to 63.9%
The advantages of significant effect.
Description of the drawings
Fig. 1 is Fe in the embodiment of the present invention 168Co10-xSi8B14Smx(x=0,2,4) XRD of ferrum-based amorphous alloy strip
Figure.
Fig. 2 is (Fe in the embodiment of the present invention 278Si9B13)1-0.01xGdx(x=0,2,4) XRD of ferrum-based amorphous alloy strip
Figure.
Fig. 3 and Fig. 4 is respectively Fe in the embodiment of the present invention 168Co10Si8B14、Fe68Co6Si8B14Sm4Fe-based amorphous alloy item
Band is under the different disposal time to the UV-Vis spectra figure of direct blue 2B solution.
Fig. 5 and Fig. 6 is respectively Fe in the embodiment of the present invention 278Si9B13、(Fe78Si9B13)0.96Gd4Fe-based amorphous alloy item
Band is under the different disposal time to the UV-Vis spectra figure of direct blue 2B solution.
Fig. 7 is Fe in the embodiment of the present invention 168Co10Si8B14Ferrum-based amorphous alloy strip repeats the dense of five dyestuffs of degradation
Degree changes with time.
Specific embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
The present embodiment Fe68Co10-xSi8B14Smx(x=0,2,4) preparation of ferrum-based amorphous alloy strip：
(1) commercially available high-purity Fe blocks, Co blocks, Si blocks, Sm blocks and FeB intermediate alloys (Fe are selected:B=79.5:20wt.%) block
As raw material, metal blocks are first subjected to surface scale disengaging and as in absolute ethyl alcohol, preventing from aoxidizing.
(2) the master alloy raw material that step (1) prepares is placed in the water jacketed copper crucible of vacuum melting furnace and repeats melting 5 times,
To ensure the uniformity of parent material, Fe-based amorphous alloy mother's ingot is obtained.
(3) alloy mother's ingot made from step (2) is polished after its surface scale, is put into single roller and gets rid of with machine (WK- II)
It is uniform using intermediate frequency furnace fusing in inert atmosphere in the quartz test tube of a diameter of 1mm of bottom opening, adjust single roller idler wheel
Linear resonance surface velocity is 42m/s, will carry out getting rid of band on copper roller idler wheel that the metal liquid after fusing is sprayed onto under inert gas shielding, make
It is about 3mm to obtain width, and thickness is about 40 μm, the Fe that length is about 5mm68Co10-xSi8B14SmxFerrum-based amorphous alloy strip.
Fe obtained by the present embodiment68Co10-xSi8B14Smx(x=0,2,4) XRD of ferrum-based amorphous alloy strip tests collection of illustrative plates such as
Shown in Fig. 1.XRD spectrum shown in FIG. 1 shows Fe68Co10Si8B14With complete amorphous feature；Fe68Co8Si8B14Sm2Have
The multiple structural features of amorphous state+α-Fe；Fe68Co6Si8B14Sm4Multiple structural features with amorphous state+α-Fe.
Fe obtained by the present embodiment68Co10Si8B14、Fe68Co6Si8B14Sm4Fe-based amorphous alloy item is containing azo dyes dirt
Application in water degradation treatment, detailed process are as follows：
(1) direct blue 2B solution is prepared using distilled water, direct blue 2B dye strength is 100mg/L in solution, for use.
(2) Fe obtained by 0.5g the present embodiment is weighed respectively68Co10Si8B14、Fe68Co6Si8B14Sm4Fe-based amorphous alloy item
Band pours into the direct blue 2B solution for the 500mL being configured, at a temperature of 35 DEG C of water bath with thermostatic control, using mechanical agitator to solution
It is stirred, the rotating speed of blender is 350r/min, extracts 4~5mL solution at regular intervals, carries out ultraviolet-visible light light
The comparison of meter is spent, as a result respectively as shown in Figure 3 and Figure 4.It is calculated by Fig. 3 results, Fe68Co10Si8B14Reaction 60 minutes it
Afterwards, dyestuff removal rate reaches 83.1%；It is calculated by Fig. 4 results, Fe68Co6Si8B14Sm4After reaction 60 minutes, dyestuff is gone
Except rate reaches 78.9%.
(3) Fe is taken out after degrading 60 minutes68Co10Si8B14Fe-based amorphous band, it is laggard with ultrasonic cleaning 10min
Second of degradation experiment of row reconfigures the direct blue 2B solution needed for as above step, is carried out with the iron-based band after cleaning
Second of degradation continuously repeats 5 above-mentioned shown degradation experiments, Fe68Co10Si8B14Fe-based amorphous band repeats degradation 5 times
The concentration versus time curve of dyestuff is for example as shown in Figure 7.As seen from Figure 7, the removal of the degradation experiment of the 1st, 3 and 5 time
Rate is 83.1%, 73.5% and 63.9% respectively.
Embodiment 2
The present embodiment (Fe78Si9B13)1-0.01xGdx(x=0,2,4) preparation of ferrum-based amorphous alloy strip：
(1) commercially available high-purity Fe blocks, Si blocks, Gd blocks and FeB intermediate alloys (Fe are selected:B=79.5:20wt.%) block conduct
Metal blocks are first carried out surface scale disengaging and as in absolute ethyl alcohol, preventing from aoxidizing by raw material.
(2) the master alloy raw material that step (1) prepares is placed in the water jacketed copper crucible of vacuum melting furnace and repeats melting 5 times,
To ensure the uniformity of parent material, Fe-based amorphous alloy mother's ingot is obtained.
(3) alloy mother's ingot made from step (2) is polished after its surface scale, is put into single roller and gets rid of with machine (WK- II)
It is uniform using intermediate frequency furnace fusing in inert atmosphere in the quartz test tube of a diameter of 1mm of bottom opening, adjust single roller idler wheel
Linear resonance surface velocity is 42m/s, will carry out getting rid of band on copper roller idler wheel that the metal liquid after fusing is sprayed onto under inert gas shielding, make
It is about 2mm to obtain width, and thickness is about 40 μm, (the Fe that length is about 5mm78Si9B13)1-0.01xGdx(x=0,2,4) it is Fe-based amorphous
Alloy strip.
(Fe obtained by the present embodiment78Si9B13)1-0.01xGdx(x=0,2,4) the XRD test collection of illustrative plates of ferrum-based amorphous alloy strip
As shown in Figure 2.XRD spectrum shown in Fig. 2 shows Fe78Si9B13With complete amorphous feature；(Fe78Si9B13)0.98Gd2Have
The multiple structural features of amorphous state+α-Fe；(Fe78Si9B13)0.96Gd4Multiple structural features with amorphous state+α-Fe.
Fe obtained by the present embodiment78Si9B13、(Fe78Si9B13)0.96Gd4Fe-based amorphous alloy item is containing azo dyes sewage
Application in degradation treatment, detailed process are as follows：
(1) direct blue 2B solution is prepared using distilled water, direct blue 2B dye strength is 100mg/L in solution, for use.
(2) Fe obtained by 0.5g the present embodiment is weighed respectively78Si9B13、(Fe78Si9B13)0.96Gd4Ferrum-based amorphous alloy strip,
The direct blue 2B solution for the 500mL being configured is poured into, at a temperature of 35 DEG C of water bath with thermostatic control, solution is carried out using mechanical agitator
Stirring, the rotating speed of blender is 350r/min, extracts 4~5mL solution at regular intervals, carries out ultraviolet-visible spectrophotometer
Comparison, as a result respectively as shown in Figure 5 and Figure 6.It is calculated by Fig. 5 results, Fe78Si9B13After reaction 60 minutes, dyestuff is gone
Except rate reaches 62.0%；It is calculated by Fig. 6 results, (Fe78Si9B13)0.96Gd4After reaction 60 minutes, dyestuff removal rate reaches
To 75.7%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
- A kind of 1. ferrum-based amorphous alloy strip, it is characterised in that the Elements Atom percentage composition of the ferrum-based amorphous alloy strip For：Fe：68%~78%, Co：0~10%, Si：8%~9%, B：12%~14%, Sm：0~4%, Gd：0~4%.
- A kind of 2. ferrum-based amorphous alloy strip according to claim 1, it is characterised in that the ferrum-based amorphous alloy strip Elements Atom percentage composition be：Fe：68%~78%, Co：6~10%, Si：8%~9%, B：12%~14%, Sm：0 ~4%.
- A kind of 3. ferrum-based amorphous alloy strip according to claim 1, it is characterised in that the ferrum-based amorphous alloy strip Elements Atom percentage composition be：Fe：68%~78%, Si：8%~9%, B：12%~14%, Gd：0~4%.
- 4. according to a kind of ferrum-based amorphous alloy strip of claims 1 to 3 any one of them, it is characterised in that described Fe-based amorphous The specification limit of alloy strip is：2~6mm of strip width, 20~100 μm of beam thickness, 1~20mm of band length.
- 5. a kind of preparation method of ferrum-based amorphous alloy strip of Claims 1 to 4 any one of them, it is characterised in that including such as Lower preparation process：(1) by Fe：68%~78%, Co：0~10%, Si：8%~9%, B：12%~14%, Sm：0~4%, Gd：0~ 4% element percentage carries out dispensing, and raw metal is carried out surface preparation；(2) it is the melting in vacuum melting furnace of step (1) pretreated raw metal is uniform, obtain alloy mother's ingot；(3) it by after alloy mother ingot progress surface preparation obtained by step (2), carries out getting rid of band by getting rid of band machine, obtains the iron-based AMORPHOUS ALLOY RIBBONS.
- 6. a kind of preparation method of ferrum-based amorphous alloy strip according to claim 5, it is characterised in that：In step (3) The linear resonance surface velocity for getting rid of band is 30~50m/s.
- 7. a kind of preparation method of ferrum-based amorphous alloy strip according to claim 5, it is characterised in that：Step (1) and Surface preparation described in step (3) refers to carry out surface scale disengaging.
- 8. a kind of preparation method of ferrum-based amorphous alloy strip according to claim 5, it is characterised in that：The iron-based is non- Peritectic alloy band has full amorphous state or the multiple structural features of amorphous state+α-Fe.
- 9. a kind of application of the ferrum-based amorphous alloy strip of Claims 1 to 4 any one of them in dyeing and printing sewage degradation treatment.
- 10. a kind of application of the ferrum-based amorphous alloy strip according to claim 9 in dyeing and printing sewage degradation treatment：It is special It levies and is in the application process, 20~1000mg/L of concentration of dyestuff, the addition of ferrum-based amorphous alloy strip in dyeing and printing sewage It measures as 0.1~100g/L, the temperature control of processing is room temperature~100 DEG C, and mechanical agitation is 0~1000r/min.
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| CN109095585A (en) * | 2018-09-30 | 2018-12-28 | 湘潭大学 | A method of for degrading azoic dye waste water |
| CN109434120A (en) * | 2018-11-14 | 2019-03-08 | 东南大学 | Fe-based amorphous alloy powder and the preparation method and application thereof for degradation of dye waste liquid |
| CN109811278A (en) * | 2019-02-28 | 2019-05-28 | 华南理工大学 | A kind of Fe-Si-B amorphous alloy strips and its preparation and the application in azo dye wastewater degradation |
| CN110918911A (en) * | 2019-11-19 | 2020-03-27 | 华南理工大学 | Iron-based series amorphous alloy strip, preparation method thereof and application thereof in degradation of azo dye wastewater |
| CN111041519A (en) * | 2019-11-21 | 2020-04-21 | 中国科学院金属研究所 | Non-noble metal amorphous electrolyzed water anode material and in-situ growth preparation method |
| CN112973691A (en) * | 2021-02-25 | 2021-06-18 | 深圳大学 | Strip amorphous alloy catalyst with nano structure and preparation method and application thereof |
| CN113201699A (en) * | 2021-04-13 | 2021-08-03 | 华南理工大学 | Iron-based alloy material and preparation method and application thereof |
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| CN109434120B (en) * | 2018-11-14 | 2021-09-03 | 东南大学 | Iron-based amorphous alloy powder for degrading dye waste liquid and preparation method and application thereof |
| CN109811278A (en) * | 2019-02-28 | 2019-05-28 | 华南理工大学 | A kind of Fe-Si-B amorphous alloy strips and its preparation and the application in azo dye wastewater degradation |
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| CN111041519A (en) * | 2019-11-21 | 2020-04-21 | 中国科学院金属研究所 | Non-noble metal amorphous electrolyzed water anode material and in-situ growth preparation method |
| CN112973691A (en) * | 2021-02-25 | 2021-06-18 | 深圳大学 | Strip amorphous alloy catalyst with nano structure and preparation method and application thereof |
| CN112973691B (en) * | 2021-02-25 | 2023-12-26 | 深圳大学 | Strip amorphous alloy catalyst with nano structure and preparation method and application thereof |
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