CN110498494A - A kind of Zero-valent Iron-mineral composite of high reduction activation and preparation method thereof - Google Patents
A kind of Zero-valent Iron-mineral composite of high reduction activation and preparation method thereof Download PDFInfo
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- CN110498494A CN110498494A CN201910708932.4A CN201910708932A CN110498494A CN 110498494 A CN110498494 A CN 110498494A CN 201910708932 A CN201910708932 A CN 201910708932A CN 110498494 A CN110498494 A CN 110498494A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Hydrology & Water Resources (AREA)
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Abstract
The present invention relates to a kind of Zero-valent Iron-mineral composites of high reduction activation, are placed in ball milling in planetary ball mill tank with Inorganic nonmetal mineral 4~10:10 in mass ratio by fe and obtain；Specific ball-milling technology condition are as follows: ratio of grinding media to material is 30~45, and Ball-milling Time is 7~8h, and rotational speed of ball-mill is 500~600rpm.The present invention selects Inorganic nonmetal mineral material and fe compatibility; and use specific ball-milling technology; Inorganic nonmetal mineral is set to form the roe shape protective layer of fine and close non crystalline structure in zeroth order iron surface; on the one hand the continued reduction ability of Zero-valent Iron is improved; in addition; Inorganic nonmetal mineral reactivity after ball milling activates is stronger, and exposes the Zero-valent Iron in composite material.
Description
Technical field
The invention belongs to water-treatment technology fields, and in particular to a kind of Zero-valent Iron-mineral composite of high reduction activation
And preparation method thereof.
Background technique
With the raising that people require living environment and conservation culture, water pollution is had been to be concerned by more and more people, water
Pollution is mainly derived from sanitary sewage, industrial wastewater and initial rainwater, and constituent is complicated in actual waste water, and what is contained largely has
Machine, inorganic pollution more cause huge threat to ecology, the health of the mankind.
Reduction precipitation method is the main chemical method of one of water pollution control process, on the basis of adding reducing agent
Degradation reduces oxidative pollutant, and is removed in the form of precipitating, and Zero-valent Iron (ZVI) is a kind of typical reducing agent.
It refers to the iron simple substance particle of certain partial size, has the characteristics that high reduction potential and reaction speed are fast, in the de- of water pollutant
Have broad application prospects in terms of except reparation with soil, have become in underground water in-situ immobilization in recent years most efficient method it
One.But high activity zeroth order iron surface is easily passivated, and micro-size fraction Zero-valent Iron itself is easily reunited, these Zero-valent Irons
Its reactivity of property defective effect itself is to limit further using for Zero-valent Iron.Researchers are to zeroth order
The preparation of iron and modified aspect have done a large amount of research, improve preparation process, are born using different type inorganic non-metallic material
Zero-valent iron-carrying, such as graphene, bentonite, chitosan and other clays, technique is substantially all with liquid-phase precipitation method under vacuum environment
Based on preparation, although the lesser product of available partial size, the reducing agents and inert protective gas etc. such as sodium borohydride are used,
Cost is excessively high to become an obstacle, is further processed in addition, preparation process can also exclude a large amount of waste water needs.Therefore, one is developed
Convenient, efficient Zero-valent Iron (ZVI) preparation method of kind becomes the task of top priority in Fe environment functional material field.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of high reduction
Active Zero-valent Iron-mineral composite and preparation method thereof is selected Inorganic nonmetal mineral material and fe compatibility, and is adopted
With specific ball-milling technology, Inorganic nonmetal mineral is made to form the roe shape protective layer of fine and close non crystalline structure in zeroth order iron surface,
Inorganic nonmetal mineral recrystallizes in water treatment procedure, the Zero-valent Iron in composite material is exposed, to keep Zero-valent Iron-mineral multiple
Condensation material can continue to keep the high reaction activity of Zero-valent Iron.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of Zero-valent Iron-mineral composite of high reduction activation is provided, is pressed by fe and Inorganic nonmetal mineral
4~10:10 of mass ratio is placed in ball milling in planetary ball mill tank and obtains；
Specific ball-milling technology condition are as follows: ratio of grinding media to material is 30~45, and Ball-milling Time is 7~8h, rotational speed of ball-mill is 500~
600rpm。
Preferably, the fe and Inorganic nonmetal mineral mass ratio are 4~10:10.
According to the above scheme, the fe and Inorganic nonmetal mineral granularity are micron order.
Preferably, the Inorganic nonmetal mineral is lime stone, dolomite, magnesite, quartz sand, kaolin, snake
One of stone or a variety of mixtures.
The invention also includes Zero-valent Iron-mineral composite preparation methods of above-mentioned high reduction activation, and specific steps are such as
Under: fe and Inorganic nonmetal mineral are placed in proportion in planetary ball mill tank and carry out ball milling, obtains the zero of high reduction activation
Valence iron-mineral composite.
The invention also includes Zero-valent Iron-mineral composite of above-mentioned high reduction activation water treatment field application.Zero
Valence iron reduction potential with higher, Eθ(Fe/Fe2+)=0.440V has very strong betatopic ability, can effectively restore
Pollutant with oxidizing property element or functional group.The Zero-valent Iron of high reduction activation provided by the invention-mineral composite wood
Material is placed in sewage, can be used for and Cr VI, azoic dye (acid red 73, methyl orange, famille rose etc.), arsenate, phosphoric acid
Salt, fluorine ion, heavy metal ion (cadmium, lead, copper, mercury etc.), nitroaromatic, halogenated aromatic compound etc. carry out reaction shape
At precipitating, then by being separated by solid-liquid separation the pollutant that can be gone in water removal.
The present invention selects Inorganic nonmetal mineral material and fe compatibility, and uses specific ball-milling technology, makes inorganic
Nonmetallic mineral forms the roe shape protective layer of fine and close non crystalline structure, inorganic non-metallic mine in water treatment procedure in zeroth order iron surface
Object recrystallization, exposes the Zero-valent Iron in composite material, so that Zero-valent Iron-mineral composite be enable to continue to keep Zero-valent Iron
High reaction activity.Zeroth order iron surface has high reaction activity in composite material, and target can be acted rapidly in water phase
Pollutant realizes efficient deoxidization, degradation.In addition, the addition of Inorganic nonmetal mineral plays vital effect wherein
Fruit, on the one hand, in product preparation process, the Inorganic nonmetal mineral effective protection high activity surface of Zero-valent Iron, and solve
When fe ball milling the problem of easy high degree of agglomeration；On the other hand, Inorganic nonmetal mineral has excellent solution buffer capacity,
It ensure that reaction front and back pH value of solution maintains neutral left and right to a certain extent, make pH value of water solution symbol when sewage discharge after handling
It closes and requires.
The ratio of Inorganic nonmetal mineral material and fe also influences the performance of composite material, and Inorganic nonmetal mineral adds
When adding very few, the zeroth order iron surface that is generated after the ball milling that cannot adequately protect；When Inorganic nonmetal mineral dosage is excessive, in water
During phase reaction, the active surface of Zero-valent Iron is unable to fully be exposed, this can all cause the reactivity of Zero-valent Iron to decline.
Alternatively, it is also possible to adjust fe and Inorganic nonmetal mineral according to the demand dealt with objects to reducing power or Precipitation Potential
Between raw material ratio, when Inorganic nonmetal mineral material is more, composite material Precipitation Potential is stronger, conversely, when fe is more,
Composite material reducing power is stronger.
The beneficial effects of the present invention are: the present invention selects Inorganic nonmetal mineral material and fe compatibility, and uses
Specific ball-milling technology makes Inorganic nonmetal mineral form the roe shape protective layer of fine and close non crystalline structure in zeroth order iron surface, and one
Aspect improves the continued reduction ability of Zero-valent Iron, in addition, the Inorganic nonmetal mineral reactivity after ball milling activates is more
By force, Inorganic nonmetal mineral recrystallizes in water treatment procedure, and recrystallization process Inorganic nonmetal mineral itself can be used as good
Good precipitating reagent, the acid radical anions such as removal contents of many kinds of heavy metal ion, arsenic phosphorus chromium, and expose the zeroth order in composite material
Iron, so that Zero-valent Iron-mineral composite be enable to continue to keep the high reaction activity of Zero-valent Iron until composite material is completely anti-
It should consume.
Detailed description of the invention
Fig. 1 be untreated raw material fe, the fe of independent ball milling, independent ball milling Inorganic nonmetal mineral with
And Zero-valent Iron-mineral composite prepared by embodiment 1 removes Cr VI effect contrast figure；
Fig. 2 be untreated raw material fe, the fe of independent ball milling, independent ball milling Inorganic nonmetal mineral with
And Zero-valent Iron-mineral composite prepared by embodiment 1 removes 73 effect contrast figure of acid red；
Fig. 3 is the SEM figure before and after raw material fe ball milling；
Fig. 4 is fe and the sample and the present embodiment Zero-valent Iron-mineral composite of Inorganic nonmetal mineral ball milling 2h
SEM figure；
Fig. 5 is that Zero-valent Iron-mineral composite sample of high reduction activation prepared by embodiment 1 carries out hexavalent chromium removal reality
The SEM of residue after testing scheme and residue point swept after full element energy disperse spectroscopy (EDS) figure；
Zero-valent Iron-mineral that Fig. 6 is untreated raw material fe, prepared by the fe of independent ball milling, embodiment 1 are multiple
Zero-valent Iron-mineral composite sample prepared by condensation material and embodiment 1 carries out the XRD of the residue after hexavalent chromium removal experiment
Figure；
Fig. 7 is untreated raw material fe, the fe (ball milling condition is same as Example 1) of independent ball milling, reality
Zero-valent Iron-mineral composite sample prepared by the Zero-valent Iron-mineral composite and embodiment 1 for applying the preparation of example 1 carries out six
Photoelectron spectroscopy (XPS) figure of residue after the removal experiment of valence chromium；
Fig. 8 is Zero-valent Iron-mineral composite of different Fe contents to hexavalent chromium removal effect picture；
Fig. 9 is Zero-valent Iron-mineral composite of different Fe contents to 73 removal effect figure of acid red.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing to the present invention make into
One step detailed description.
Fe partial size used in the embodiment of the present invention be 300 mesh, Inorganic nonmetal mineral used with lime stone it is main at
Divide for calcium carbonate, partial size is micron order.
Embodiment 1
Zero-valent Iron-mineral composite preparation of high reduction activation, the specific steps are as follows:
Fe and Inorganic nonmetal mineral 4.3:10 in mass ratio are weighed, iron content is kept to account for the 30% of gross sample, altogether
It weighs 2g sample to be put into ball grinder, ratio of grinding media to material is controlled 35, and revolving speed is set as 500rpm, Ball-milling Time 8h, is obtained high also
Former active Zero-valent Iron-mineral composite, the composite material of preparation is taken out, and is saved under the conditions of hermetically drying.
Test the d of Zero-valent Iron-mineral composite manufactured in the present embodiment10、d50And d90, and with simple substance iron material, list
Only fe (ball milling condition is identical as the present embodiment) of ball milling and the sample of fe and Inorganic nonmetal mineral ball milling 2h
(remaining condition is identical as the present embodiment) is compareed, and partial size comparison is shown in Table 1.
Table 1
The partial size of the fe of independent ball milling becomes very uneven as can be seen from Table 1, d50It becomes much larger instead, and with
Sample particle diameter after Inorganic nonmetal mineral mixing and ball milling is relatively uniform, and Inorganic nonmetal mineral prevents the reunion of fe.
SEM figure before and after raw material fe ball milling is shown in (a) and (b) in Fig. 3, it can be seen that circle is presented in the zero-valent iron particle before ball-milling treatment
Spherical, the serious reunion of sample appearance after ball milling of profit, and reuniting with surface passivation is the main of influence Zero-valent Iron reduction activation
Reason.
It can be seen that in table 1, fe and Inorganic nonmetal mineral ball milling 8h are compared with ball milling 2h, and effect is more preferable, and gained is multiple
The decline of condensation material partial size, in Fig. 4 (c) and (d) be respectively above-mentioned fe and Inorganic nonmetal mineral ball milling 2h sample with
Embodiment Zero-valent Iron-mineral composite SEM figure is still deposited by image it is seen that mixing sample surfaces under 2h ball milling condition
In some Inorganic nonmetal mineral cubic crystals, and when Ball-milling Time extends to 8h, the cubic crystal appearance base on aggregate sample surface
This disappearance, Inorganic nonmetal mineral forms fine and close roe shape protective layer in zeroth order iron surface, to protect newly-generated zeroth order
Iron surface.
Embodiment 2
Cr VI measure of merit in the Zero-valent Iron of high reduction activation-mineral composite pollution administration water body
Chromate waste water, solution ph 6.72, temperature are simulated with the potassium bichromate solution that 100ml hexavalent chromium concentration is 10mg/L
Degree is 25 DEG C, Zero-valent Iron-mineral composite sample of high reduction activation prepared by 0.1g embodiment 1 is added, being put into revolving speed is
Half an hour is vibrated in the oscillator of 250r/min, is periodically sampled, and the removal effect of determination of hexavalent chromium.
As control, respectively by the nothing of untreated raw material fe, the fe of independent ball milling and independent ball milling
Machine nonmetallic mineral (fe and inorganic non-metallic ball milling condition are same as Example 1) carries out above-mentioned Cr VI by equal conditions
Removal experiment, four kinds of samples removal Cr VI effect contrast figures see Fig. 1, relative to untreated fe, independent ball milling
The Inorganic nonmetal mineral of Zero-valent Iron and independent ball milling, embodiment 1 add Inorganic nonmetal mineral mixing and ball milling after it is compound
Material has significant raising to the removal effect of Cr VI, reaches after reacting 30min to the removal effect of Cr VI
99.68%.
Zero-valent Iron-mineral composite (Ball-milling Time 8h) and fe and inorganic non-metallic prepared by comparative example 1
Sample (remaining condition is same as Example 1) hexavalent chromium removal effect of mineral ball milling 2h is with 100ml hexavalent chromium concentration
The potassium bichromate solution of 10mg/L simulates chromate waste water, solution ph 6.72, and temperature is 25 DEG C, and the processing time is half small
When, two kinds of samples are compared under Different adding amount to the removal rate of chromium, and test result is shown in Table 2.
Table 2
As can be seen from Table 2, under the conditions of same additive amount, removal of the sample that embodiment 1 is obtained through ball milling 8h to chromium
Effect is substantially better than the sample of ball milling 2h.
In Fig. 5 (e) and (f) be respectively high reduction activation prepared by embodiment 1 Zero-valent Iron-mineral composite sample into
The SEM figure and full element energy disperse spectroscopy (EDS) figure after sweeping to residue point of residue after the experiment of row hexavalent chromium removal, figure (e) can
To find out, the decrystallized Inorganic nonmetal mineral after ball milling recrystallizes after the reaction, fine and close covering originally after ball milling
Recrystallizing in the ironing surface Inorganic nonmetal mineral of zeroth order can allow the surface of Zero-valent Iron to be exposed again in aqueous solution,
It ensure that the lasting progress of reaction, figure (f), which is also confirmed that, is successfully reduced to trivalent chromium in the surface hexavalent chromium of sample.
By aforementioned untreated raw material fe, the fe (ball milling condition is same as Example 1) of independent ball milling, reality
Zero-valent Iron-mineral composite sample prepared by the Zero-valent Iron-mineral composite and embodiment 1 for applying the preparation of example 1 carries out six
Valence chromium removal experiment after residue carry out X-ray diffraction test, XRD diagram as shown in fig. 6, the sample of embodiment 1 there is no Fe's
Other objects mutually generate, and Fe is not chemically reacted with Inorganic nonmetal mineral before and after this shows ball milling, inorganic non-metallic mine
Physics coating function only has occurred in object and Fe.Inorganic nonmetal mineral is presented decrystallized after ball milling, and hexavalent chromium removal
Occurs the diffraction maximum of Inorganic nonmetal mineral in the image of residue after experiment again, this and scanning electron microscopy before
The conclusion of mirror test is consistent.
Untreated raw material fe, the fe (ball milling condition is same as Example 1) of independent ball milling, embodiment 1
Zero-valent Iron-mineral composite sample of Zero-valent Iron-mineral composite and embodiment 1 preparation of preparation carries out Cr VI and goes
Except photoelectron spectroscopy (XPS) figure of the residue after experiment is as shown in fig. 7, in raw material simple substance it can be seen from the narrow spectrum swarming of Fe
There is no Fe at the 706eV of residue (d) after iron (a) and hexavalent chromium removal experiment0Information exist, this shows the list without ball milling
Matter iron surface is passivated layer encirclement, and active Zero-valent Iron is not exposed adequately, on the other hand also turns out that reduction is anti-
It should be in the process that Zero-valent Iron is playing a leading role, the Zero-valent Iron that surface is exposed after reaction is also consumed totally.From list
Zero-valent Iron-mineral composite (c) image prepared by the fe (b) and embodiment 1 of only ball milling can be found that both samples
Surface composition it is complex, there are also a small amount of divalent and trivalent Fe to exist other than Zero-valent Iron.In addition, hexavalent chromium removal is tested
Residue surface also fits the information of FeOOH afterwards, this may be caused by the aqueous phase reactions of Zero-valent Iron and Cr VI.
Embodiment 3
The measure of merit of acid red 73 in the Zero-valent Iron of high reduction activation-mineral composite pollution administration water body
Azoic dye waste water, solution ph are simulated with 73 solution of acid red that 73 concentration of 100ml acid red is 50mg/L
It is 6.55, temperature is 25 DEG C, Zero-valent Iron-mineral composite sample of high reduction activation prepared by 0.03g embodiment 1 is added,
It is put into the oscillator that revolving speed is 250r/min and vibrates half an hour, periodically sample, and the removal effect of determination of hexavalent chromium.
As control, respectively by the nothing of untreated raw material fe, the fe of independent ball milling and independent ball milling
Machine nonmetallic mineral (fe and inorganic non-metallic ball milling condition are same as Example 1) carries out above-mentioned acid red by equal conditions
73 removal experiments, four kinds of sample removal 73 effect contrast figures of acid red see Fig. 2, relative to untreated fe, independent ball
The Inorganic nonmetal mineral of the Zero-valent Iron of mill and independent ball milling, after embodiment 1 adds Inorganic nonmetal mineral mixing and ball milling
Composite material has significant raising to the removal effect of acid red 73, reaches after reacting 30min to the removal effect of acid red 73
To 99.98%.
Zero-valent Iron-mineral composite (Ball-milling Time 8h) and fe and inorganic non-metallic prepared by comparative example 1
The sample (remaining condition is same as Example 1) of mineral ball milling 2h is to 73 removal effect of acid red, with 73 concentration of 100ml acid red
Azoic dye waste water, solution ph 6.55 are simulated for the potassium bichromate solution of 50mg/L, temperature is 25 DEG C, and the processing time is equal
For half an hour, two kinds of samples are compared under Different adding amount to the removal rate of acid red 73, test result is shown in Table 3.
Table 3
As can be seen from Table 3, under the conditions of same additive amount, the sample that embodiment 1 is obtained through ball milling 8h is to acid red 73
Removal effect be substantially better than the sample of ball milling 2h.
Embodiment 4
Zero-valent Iron-mineral composite preparation of different Fe contents, the specific steps are as follows:
Fe and Inorganic nonmetal mineral are mixed by different proportion, are prepared using the ball grinding method of embodiment 1
Different Zero-valent Iron-the mineral composite of one group of iron content, wherein Fe content is respectively 10%, 20%, 30%, 40%, 50%,
60%, 70%.
Zero-valent Iron-mineral composite of different Fe contents is tested to hexavalent chromium removal effect
Hexavalent chromium removal test is carried out using method same as Example 2, is 10mg/L's with 100ml hexavalent chromium concentration
Potassium bichromate solution simulates chromate waste water, and Zero-valent Iron-mineral composite sample is added to simulated wastewater by different dosages
In, final hexavalent chromium removal effect is shown in Fig. 8, it can be found that after Fe amount is higher than 40% in Zero-valent Iron-mineral composite sample, In
In the case of same injected volume, hexavalent chromium removal rate is almost unchanged.Within the scope of 0.1~1.0g/L, Cr VI is gone sample injected volume
Except rate is increased as injected volume increases.
Zero-valent Iron-mineral composite of different Fe contents is tested to 73 removal effect of acid red
The removal test of acid red 73 is carried out using method same as Example 3, is with 73 concentration of 100ml acid red
The potassium bichromate solution of 50mg/L simulates chromate waste water, and Zero-valent Iron-mineral composite sample is added to by different dosages
In simulated wastewater, final 73 removal effect of acid red is shown in Fig. 9, it can be seen that in same injected volume, sample ratio containing Fe
Composite material is best to the removal effect of acid red 73 when being 50%, and concentration is further added by, and removal rate declines instead, sample injected volume
Within the scope of 0~0.30g/L, 73 removal rate of acid red is increased as injected volume increases.
Claims (6)
1. a kind of Zero-valent Iron-mineral composite of high reduction activation, which is characterized in that it is by fe and inorganic non-metallic mine
Object 4~10:10 in mass ratio is placed in ball milling in planetary ball mill tank and obtains；
Specific ball-milling technology condition are as follows: ratio of grinding media to material is 30~45, and Ball-milling Time is 7~8h, and rotational speed of ball-mill is 500~600rpm.
2. Zero-valent Iron-mineral composite of high reduction activation according to claim 1, which is characterized in that the simple substance
Iron and Inorganic nonmetal mineral mass ratio are 4~10:10.
3. Zero-valent Iron-mineral composite of high reduction activation according to claim 1, which is characterized in that the simple substance
Iron and Inorganic nonmetal mineral granularity are micron order.
4. Zero-valent Iron-mineral composite of high reduction activation according to claim 1, which is characterized in that described inorganic
Nonmetallic mineral is lime stone, dolomite, magnesite, quartz sand, kaolin, one of serpentine or a variety of mixtures.
5. a kind of Zero-valent Iron-mineral composite preparation method of any high reduction activation of claim 1-4, special
Sign is, the specific steps are as follows: fe and Inorganic nonmetal mineral are placed in proportion in planetary ball mill tank and carry out ball milling, is obtained
To Zero-valent Iron-mineral composite of high reduction activation.
6. a kind of Zero-valent Iron-mineral composite of any high reduction activation of claim 1-4 is in water treatment field
Using.
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| CN113184945A (en) * | 2021-04-28 | 2021-07-30 | 中国地质科学院水文地质环境地质研究所 | Environment-friendly iron-based mineral composite material and preparation method and application thereof |
| CN113184945B (en) * | 2021-04-28 | 2023-01-31 | 中国地质科学院水文地质环境地质研究所 | Environment-friendly iron-based mineral composite material and preparation method and application thereof |
| CN114522726A (en) * | 2022-03-03 | 2022-05-24 | 武汉理工大学 | Reduced iron powder composite polytetrafluoroethylene material and preparation method and application thereof |
| CN114522726B (en) * | 2022-03-03 | 2023-08-25 | 武汉理工大学 | Reduced iron powder composite polytetrafluoroethylene material and preparation method and application thereof |
| CN114789040A (en) * | 2022-04-28 | 2022-07-26 | 辽宁石油化工大学 | Ball-milled zero-valent iron-doped sulfur/biochar composite material and preparation method and application thereof |
| CN114789040B (en) * | 2022-04-28 | 2023-11-17 | 辽宁石油化工大学 | Ball-milling zero-valent iron sulfur/biochar doped composite material and preparation method and application thereof |
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