CN107119223A - It is a kind of for the material and preparation method of sewage disposal and application - Google Patents
It is a kind of for the material and preparation method of sewage disposal and application Download PDFInfo
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- CN107119223A CN107119223A CN201710230896.6A CN201710230896A CN107119223A CN 107119223 A CN107119223 A CN 107119223A CN 201710230896 A CN201710230896 A CN 201710230896A CN 107119223 A CN107119223 A CN 107119223A
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- sewage disposal
- ball
- sewage
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- ball milling
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 239000010865 sewage Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 38
- 238000000498 ball milling Methods 0.000 claims description 32
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 62
- 229910052742 iron Inorganic materials 0.000 abstract description 17
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 239000000987 azo dye Substances 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000007496 glass forming Methods 0.000 abstract description 4
- 239000010842 industrial wastewater Substances 0.000 abstract description 4
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/048—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by pulverising a quenched ribbon
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a kind of for the material and preparation method of sewage disposal and application, wherein, the chemical formula of the material for sewage disposal is：FeaSibBcMd, wherein, M is one kind in Nb, Mo, Y, Hf, Er, Ta, Cu, 70≤a≤84,6≤b≤30,10≤c≤20,0≤d≤3, a+b+c+d=100.Due to containing iron in the sewage-treating agent, this can occur redox reaction with N=N double bonds in azo dyes, so as to destroy to biological toxic N=N double bond groups, and other elements in sewage-treating agent, iron can be induced quickly to degrade N=N double bond groups, glass forming ability and corrosion resistance etc. can also be improved.By the way that above-mentioned sewage-treating agent is applied in sewage disposal, especially to the industrial wastewater containing azo dyes, with higher degradation rate, more preferable sewage treatment function.
Description
Technical field
The present invention relates to sewage treatment area, more particularly to a kind of material and preparation method for sewage disposal is with answering
With.
Background technology
At present, the waste water containing azo dyes of the industry such as weaving, leather, papermaking, printing discharge is to water resource and ring
Border causes heavy damage.Azo dyes is in dye industry proportion more than 50%.Therefore economic, environmental protection, efficiently processing are even
Nitrogen waste water from dyestuff has important practical significance.
Traditional treatment method of printing and dying wastewater has：Physical (porous material absorption such as activated carbon), chemical method (zero-valent state gold
Category degraded, such as zeroth order Fe) and biotechnology method (microbial degradation), wherein technique mainly includes activated sludge process, life
Thing membrane process, anaerobic-aerobic disposal and biological iron process etc., most of conventional physicals and chemical process are by absorption, sunk
Drop technology shifts pollutant, but easily causes secondary pollution and can not realize thorough degraded, and also has the following disadvantages：1) it is dirty
Mud amount is excessive, it is possible to produce the larger intermediate of toxicity；2) waste water (temperature, solution ph and the oxygen content to changing greatly
Deng) lacking adaptability, application is narrow；3) sewage disposal device (pond) floor space is huge, and operation, maintenance cost are higher,
It is difficult to receive for many medium-sized and small enterprises.There is colourity in bioanalysis and COD removal efficiencies are not high, and the reaction time is long, typically
It is not used alone.In addition, the conventional method of the above all can not easily reclaim sewage-treating agent, and processing cost is high.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of material and system for sewage disposal
Preparation Method and application, it is intended to solve when existing sewage-treating agent is used by temperature limiting, efficiency is low, costly and is difficult to
The problem of collecting recovery etc..
Technical scheme is as follows：
A kind of material for sewage disposal, wherein, the chemical formula of the material for sewage disposal is：FeaSibBcMd, its
In, M is one kind in Nb, Mo, Y, Hf, Er, Ta, Cu, 70≤a≤84,6≤b≤30,10≤c≤20,0≤d≤3, a+b+c+
d=100。
The described material for sewage disposal, wherein, the chemical formula of the material for sewage disposal is：
Fe75Si8B15Nb2Or Fe75Si8B15Y2。
The described material for sewage disposal, wherein, the material is shaped to particulate powder.
The described material for sewage disposal, wherein, the particle diameter of the particulate powder is 10-40 μm.
As above a kind of preparation method of the material for sewage disposal described in any one, wherein, comprise the following steps：
Step A, according to mentioned component proportioning carry out dispensing, obtain mixed material；
Step B, mixed material is subjected to melting, obtains alloy pig；
Step C, by alloy pig carry out get rid of band, obtain strip；
Step D, strip ball clayed into power, obtain described being used for the material of sewage disposal.
The preparation method of the described material for sewage disposal, wherein, in the step B, using arc melting institute
State mixing batch mixing；Wherein, the temperature of the melting is 1000-1800 DEG C, and the number of times of the melting is 3-8 times.
The preparation method of the described material for sewage disposal, wherein, in the step C, band is got rid of using copper roller described
Alloy pig；Wherein, the linear velocity that the copper roller gets rid of band is 20-50m/s.
The preparation method of the described material for sewage disposal, wherein, in the step C, the thickness of the strip is
10-100μm。
The preparation method of the described material for sewage disposal, wherein, in the step D, ball milling under an inert atmosphere
The strip, the ball grinder that the ball milling is used is adopted for stainless steel jar mill or stainless steel inner sleeve corundum ball grinder, the ball milling
Abrading-ball is stainless steel ball or zirconia ball, and the time of the ball milling is 10-100h.
Described in a kind of as above any one for sewage disposal material application, wherein, by described for sewage disposal
Materials application is in sewage disposal.
Beneficial effect：The present invention is by iron, silicon, boron amorphous powder and trace rare-earth element for the material of sewage disposal
Coordinate what is be made, due to containing iron in the sewage-treating agent, it is anti-that this can occur redox with the-N in azo dyes=N- double bonds
Should, so that destroy to biological toxic-N=N- double bond groups, and other elements in sewage-treating agent, iron can be induced more
Degraded-N=N- double bond groups, and improve glass forming ability and corrosion resistance etc. soon.By by amorphous state iron-based mixed-powder
Apply in sewage disposal, especially to the industrial wastewater containing azo dyes, with higher degradation rate, serve more preferably
Sewage treatment function.In addition, the material preparation cost of the present invention for sewage disposal is low, and also allow for collecting, be beneficial to
Resource reclaim.
Brief description of the drawings
Fig. 1 is the Fe for preparing in embodiment 175Si8B15Nb2The XRD phenograms of amorphous powder.
Fig. 2 is the Fe for preparing in embodiment 175Si8B15Nb2The SEM phenograms of amorphous powder.
Fig. 3 is the Fe for preparing in embodiment 175Si8B15Nb2Another SEM phenograms of amorphous powder.
Fig. 4 is the Fe for preparing in embodiment 275Si8B15Y2The XRD phenograms of amorphous powder.
Fig. 5 is the Fe for preparing in embodiment 275Si8B15Y2The SEM phenograms of amorphous powder.
Fig. 6 is the Fe for preparing in embodiment 275Si8B15Y2Another SEM phenograms of amorphous powder.
Fig. 7 is Fe in embodiment 375Si8B15Nb2UV absorption microphotohram of the amorphous powder to methyl orange solution.
Fig. 8 is Fe in embodiment 375Si8B15Nb2Amorphous powder is to methyl orange solution percent of decolourization schematic diagram.
Embodiment
The present invention provides a kind of for the material and preparation method of sewage disposal and application, to make the purpose of the present invention, skill
Art scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that tool described herein
Body embodiment only to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of material for sewage disposal, wherein, contain iron in the material for sewage disposal
（Fe）, silicon（Si）And boron（B）Amorphous Fe based powders, can also contain trace rare-earth element.Specifically, it is of the present invention to be used for
The chemical formula of the material of sewage disposal is：FeaSibBcMd, wherein, M is one kind in Nb, Mo, Y, Hf, Er, Ta, Cu, 70≤a
≤ 84,6≤b≤30,10≤c≤20,0≤d≤3, a+b+c+d=100.Due to the sewage-treating agent（It is i.e. described to be used at sewage
The material of reason）In contain iron, this can occur redox reaction with the-N in azo dyes=N- double bonds, so as to destroy to biology
Toxic-N=N- double bond groups, and silicon and boron in sewage-treating agent, can induce iron quickly to degrade-N=N- double bond bases
Trace rare-earth element in group, sewage-treating agent, can improve glass forming ability and corrosion resistance etc..All addition element are all
Belong to environment-friendly element, do not result in secondary pollution.By the way that amorphous state iron-based mixed-powder is applied in sewage disposal, especially
It is to the industrial wastewater containing azo dyes, with higher degradation rate, more preferable sewage treatment function.Further, since
Raw material is relatively inexpensive, and the proportioning between amorphous powder has wider composition range, it is easier to by regulating and controlling material composition ratio
Example regulates and controls the degradation rate in practical application.Material preparation cost of the present invention for sewage disposal is low, and also allows for
Collect, beneficial to resource reclaim.
A kind of specific embodiment for material for sewage disposal that the present invention is provided, wherein, it is described to be used for sewage disposal
The chemical formula of material can be Fe75Si8B15Nb2Or Fe75Si8B15Y2.The present invention this be used for the material of sewage disposal by iron,
The amorphous Fe based powders such as silicon, boron are made, and it has higher chemism, and the degradation efficiency of azo dyes is high；In addition, adding
Added elements Nb or Y can improve iron based metallic glass（That is the material for sewage disposal）Forming ability, moreover it is possible to it is certain
The corrosion resistance of iron based metallic glass is improved in degree；And can be by regulating and controlling material composition ratio（That is iron powder, silica flour and boron powder
Proportioning）To regulate and control the degradation efficiency of sewage disposal.
Preferably, the material of the present invention for sewage disposal is shaped to particulate powder, the particulate powder
Particle diameter is 10-40 μm.Wherein, the particle diameter of particulate powder is smaller, and specific surface area is bigger, is more conducive to improving reaction rate；But
Be particulate powder particle diameter it is too small, easily reunite between powder, be unfavorable for powder and be uniformly dispersed in sewage.Meanwhile, if
The particle diameter of particulate powder is less than 10 μm, it is necessary to extend High Energy Ball Milling Time, reduces the production efficiency of the inorganic agent and gives birth to it
Produce cost increase.Through considering, the optimum grain-diameter of the particulate powder is limited to 10-40 μm by the present invention.
The preparation method that the present invention also provides the material for sewage disposal described in a kind of as above any one is preferably implemented
Example, wherein, comprise the following steps：
Step A, according to mentioned component proportioning carry out dispensing, obtain mixed material；
In the step A, matched according to mentioned component, i.e., according to FeaSibBcMdIn each component atoms than carrying out dispensing, obtain institute
State mixed material.
Step B, mixed material is subjected to melting, obtains alloy pig；
In the step B, using mixing batch mixing described in arc melting；Wherein, the temperature of the melting is 1000-1800 DEG C
（Such as 1400 DEG C）, the number of times of the melting is 3-8 times, and melt back 3-8 times is in order that each area's composition of alloy is uniform.
Step C, by alloy pig carry out get rid of band, obtain strip；
In the step C, got rid of using copper roller with the alloy pig, obtain the strip of 10-100 μm of thickness；Wherein, the copper roller is got rid of
The linear velocity of band is 20-50m/s（Such as 36m/s）, the linear velocity of the scope is in order that melt has enough cooldown rates, with shape
Into amorphous state.
Step D, strip ball clayed into power, obtain described being used for the material of sewage disposal.
In the step D, in inert atmosphere（Such as argon gas）Strip described in lower ball milling, obtains the material for sewage disposal
Material.The present invention can prevent that powder is oxidized in mechanical milling process using ball milling in an inert atmosphere.Specifically, the ball milling is adopted
Ball grinder can be stainless steel jar mill or stainless steel inner sleeve corundum ball grinder, and the abrading-ball that the ball milling is used can be for not
Become rusty steel ball or zirconia ball, and ratio of grinding media to material can be（8-12）:1（Such as 10:1）, the rotating speed of ball milling can be 300-350r/min（Such as
300r/min）, the time of the ball milling is 10-100h（Such as 50h）, turn 24 minutes during ball milling, stop 24 minutes, be to prevent
The energy produced during ball milling makes non crystalline structure change, and obtains the material for sewage disposal that particle diameter is 10-40 μm.
The present invention uses ball-milling method, within the above-mentioned time, you can prepares the less particulate powder of particle diameter, considerably increases powder
Specific surface area, and specific surface area is bigger, more beneficial to raising degradation efficiency.And the powder rough surface obtained using ball-milling method, slightly
Rough powder surface further increases its specific surface area, while substantially increasing reaction efficiency.
The present invention also provides a kind of application for the material for being used for sewage disposal described in as above any one, wherein, used described
In sewage disposal materials application in sewage disposal, be particularly applied to the sewage disposal containing azo dyes.It is of the present invention to use
There is higher chemism in the material of sewage disposal, the degradation efficiency of azo dyes is high.
With reference to embodiment, the present invention is described in detail.
Embodiment 1
Material Fe for sewage disposal75Si8B15Nb2Preparation, comprise the following steps that：
By atomic ratio Fe:B:Si:Nb=75:15:8:2 carry out dispensing, mixed material are obtained, by mixed material in electric arc furnaces
Melt back 4 times, obtain alloy pig at 1400 DEG C, alloy pig are got rid of into band using copper roller, the linear velocity that the copper roller gets rid of band is every
36 meters of second, the strip that thickness is 20 microns is fabricated to, strip ball milling is finally subjected under an inert atmosphere, ratio of grinding media to material is 10:1,
The rotating speed of ball milling is 300r/min, time of ball milling be 50h, ball milling during turn 24 minutes, stop 24 minutes, obtain 30 μm
Fe75Si8B15Nb2(at.%) powder.Fe after ball milling75Si8B15Nb2(at.%) XRD of powder, which is characterized, sees Fig. 1；After ball milling
Fe75Si8B15Nb2The SEM of powder, which is characterized, sees Fig. 2 and Fig. 3, and from Fig. 2 and Fig. 3, the powder surface obtained using ball-milling method is thick
Rough, coarse powder surface further increases its specific surface area, while substantially increasing degradation efficiency.
Embodiment 2
Material Fe for sewage disposal75Si8B15Y2Preparation, comprise the following steps that：
By atomic ratio Fe:B:Si:Y=75:15:8:2 carry out dispensing, mixed material are obtained, by mixed material 1400 in electric arc furnaces
Melt back 4 times, obtain alloy pig at DEG C, alloy pig are got rid of into band using copper roller, the linear velocity that the copper roller gets rid of band is per second 36
Rice, is fabricated to the strip that thickness is 25 microns, strip is finally carried out into ball milling under an argon atmosphere, ratio of grinding media to material is 10:1, ball milling
Rotating speed be 300r/min, time of ball milling be 50h, ball milling during turn 24 minutes, stop 24 minutes, obtain 40 μm
Fe75Si8B15Y2(at.%) powder.Fe after ball milling75Si8B15Y2The XRD of powder, which is characterized, sees Fig. 4.Fe after ball milling75Si8B15Y2Powder
SEM characterize and see Fig. 5 and Fig. 6, from Fig. 5 and Fig. 6, the powder rough surface that ball-milling method is obtained, and coarse surface enters one
Step improves its specific surface area, substantially increases degradation reaction efficiency.
Embodiment 3
Accurately weigh the Fe prepared in embodiment 175Si8B15Nb2Powder 0.16g, puts molten to 40mL (20mg/L) methyl orange is filled
In the instrument of liquid, stand at normal temperatures and pressures, supernatant liquor is taken at regular intervals, do ultraviolet spectrometry detection.Testing result
As shown in fig. 7, after 2h, degraded is completed.With the passage of degradation time, the methyl orange characteristic absorption peak intensity at 464nm
Increase with the time and reduce, finally disappear, show that the azo double bond of methyl orange is destroyed；Small peak at 273nm floats to the left
Move at 246nm, show to have the compound of the functional group containing phenyl ring to be increasingly generated with degradation process.According to degradation rate formula D=(A0-
At)/A0(A0For initial strength, AtFor Real-time intensity) percent of decolourization of the sewage-treating agent to methyl orange can be obtained, as shown in Figure 8.
In summary, what the present invention was provided is a kind of for the material and preparation method of sewage disposal and application, institute of the present invention
The chemical formula for stating the material for sewage disposal is：FeaSibBcMd, wherein, M is one kind in Nb, Mo, Y, Hf, Er, Ta, Cu,
70≤a≤84,6≤b≤30,10≤c≤20,0≤d≤3, a+b+c+d=100.Due to containing iron in the sewage-treating agent, this
Can occur redox reaction with the-N in azo dyes=N- double bonds, so as to destroy to biological toxic-N=N- double bond bases
Group, and silicon and boron in sewage-treating agent can induce iron quickly to degrade-N=N- double bond groups, micro- in sewage-treating agent
Rare earth element is measured, glass forming ability and corrosion resistance etc. can be improved.By the way that amorphous state iron-based mixed-powder is applied in dirt
In water process, especially to the industrial wastewater containing azo dyes, with higher degradation rate, more preferable sewage disposal work(
Energy.Further, since raw material is relatively inexpensive, the proportioning between amorphous powder has wider composition range, it is easier to by adjusting
Material composition ratio is controlled to regulate and control the degradation rate in practical application.Material of the present invention for sewage disposal prepares cost
It is low, and also allow for collecting, beneficial to resource reclaim.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (10)
1. a kind of material for sewage disposal, it is characterised in that the chemical formula of the material for sewage disposal is：
FeaSibBcMd, wherein, M is one kind in Nb, Mo, Y, Hf, Er, Ta, Cu, 70≤a≤84,6≤b≤30,10≤c≤20,0
≤ d≤3, a+b+c+d=100.
2. the material according to claim 1 for sewage disposal, it is characterised in that the material for sewage disposal
Chemical formula be：Fe75Si8B15Nb2Or Fe75Si8B15Y2。
3. the material according to claim 1 or 2 for sewage disposal, it is characterised in that the material is shaped to particle
Sprills.
4. the material according to claim 3 for sewage disposal, it is characterised in that the particle diameter of the particulate powder is
10-40μm。
5. a kind of preparation method of material for sewage disposal as described in claim any one of 1-4, it is characterised in that bag
Include following steps：
Step A, according to mentioned component proportioning carry out dispensing, obtain mixed material；
Step B, mixed material is subjected to melting, obtains alloy pig；
Step C, by alloy pig carry out get rid of band, obtain strip；
Step D, strip ball clayed into power, obtain described being used for the material of sewage disposal.
6. the preparation method of the material according to claim 5 for sewage disposal, it is characterised in that in the step B,
Using mixing batch mixing described in arc melting；Wherein, the temperature of the melting is 1000-1800 DEG C, and the number of times of the melting is
3-8 times.
7. the preparation method of the material according to claim 5 for sewage disposal, it is characterised in that in the step C,
Got rid of using copper roller with the alloy pig；Wherein, the linear velocity that the copper roller gets rid of band is 20-50m/s.
8. the preparation method of the material according to claim 5 for sewage disposal, it is characterised in that in the step C,
The thickness of the strip is 10-100 μm.
9. the preparation method of the material according to claim 5 for sewage disposal, it is characterised in that in the step D,
Strip described in ball milling under an inert atmosphere, the ball grinder that the ball milling is used is stainless steel jar mill or stainless steel inner sleeve corundum ball
Grinding jar, the abrading-ball that the ball milling is used is stainless steel ball or zirconia ball, and the time of the ball milling is 10-100h.
10. a kind of application for the material for being used for sewage disposal as described in any one of claim 1 ~ 4, it is characterised in that will be described
Materials application for sewage disposal is in sewage disposal.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070236A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院金属研究所 | Ferrum-based amorphous alloy strip for treating printing and dyeing wastewater and preparation method thereof |
| CN102383069A (en) * | 2011-10-19 | 2012-03-21 | 无锡华冶钢铁有限公司 | Iron-based amorphous alloy used for printing and dying wastewater treatment |
| CN105314726A (en) * | 2014-07-01 | 2016-02-10 | 中国科学院宁波材料技术与工程研究所 | Printing and dyeing wastewater treatment method |
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|---|---|---|---|---|
| CN102070236A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院金属研究所 | Ferrum-based amorphous alloy strip for treating printing and dyeing wastewater and preparation method thereof |
| CN102383069A (en) * | 2011-10-19 | 2012-03-21 | 无锡华冶钢铁有限公司 | Iron-based amorphous alloy used for printing and dying wastewater treatment |
| CN105314726A (en) * | 2014-07-01 | 2016-02-10 | 中国科学院宁波材料技术与工程研究所 | Printing and dyeing wastewater treatment method |
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| SHENGHUI XIE等: "A highly efficient degradation mechanism of methyl orange using Fe-based metallic glass powders", 《SCIENTIFIC REPORTS》 * |
| 黄平: "FeBSiY金属玻璃降解偶氮染料的效率及影响因素研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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