CN109911992B - Preparation method and application of iron-based multi-metal alloy micro-electrolysis filler - Google Patents
Preparation method and application of iron-based multi-metal alloy micro-electrolysis filler Download PDFInfo
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Abstract
The invention discloses a preparation method and application of an iron-based multi-metal alloy micro-electrolysis filler, aiming at the problems that the existing iron-carbon micro-electrolysis filler is easy to harden and has low treatment efficiency in wastewater treatment, iron powder and one or two metal catalytic components of copper, nickel, zinc and manganese are ball-milled by a mechanochemical method to prepare iron-based multi-metal alloy powder, then the iron-based multi-metal alloy powder, carbon, clay, pore-forming agent and other raw materials are mixed, a proper amount of water and a bonding agent are added to prepare raw material balls after the procedures of kneading, cutting, granulating, polishing and the like, and the raw material balls are continuously sintered in an anoxic atmosphere to form the iron-based multi-metal alloy micro-electrolysis filler with higher strength. The micro-electrolysis filler prepared by the invention can be used for pretreatment of industrial wastewater of printing and dyeing, chemical industry, electroplating, papermaking and the like before biochemical treatment process, and can also be used in the field of wastewater treatment such as advanced treatment of sewage treatment plants and the like.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a catalytic reduction pretreatment material for industrial wastewater and an application method thereof.
Background
In the field of sewage treatment, the water treatment process in China is mainly based on a biological method, but toxic organic matters and organic matters which are difficult to degrade in industrial wastewater are often difficult to treat and discharge according to the standard by the biological method, and even chemical oxidation is adopted, part of macromolecular organic matters are difficult to completely degrade into inorganic matters. However, most of the toxic and non-degradable organic matters are relatively easy to be chemically reduced, and the toxic effect of the reduction products on microorganisms is greatly reduced, so that the biodegradability of the waste water is improved.
At present, the mature chemical reduction process studied at home and abroad is an iron-carbon micro-electrolysis method, the mechanism of which mainly comprises the electrochemical catalysis of a cathode, direct reduction of iron, reduction of nascent state H, polymerization and precipitation of a hydroxyl iron complex and the like, and engineering application shows that the method has a good effect on removing refractory organic pollutants in industrial wastewater such as dye wastewater, printing and dyeing wastewater, papermaking wastewater, chemical wastewater and the like. For example, the refractory pollutants in the dye wastewater are mainly derived from azo organic pollutants of azo dyes, the azo substances not only have specific colors, but also have complex molecular structures and poor biodegradability, most of the azo substances have potential toxicity, and azo bonds in the azo substances have electron-withdrawing property and are not easy to oxidize and degrade. On the contrary, the aromatic amine generated by breaking the azo bond after reduction is easily oxidized or degraded by aerobic microorganisms, and has a good decoloring effect.
However, with the development of iron-carbon micro-electrolysis technology, the defects of the iron-carbon micro-electrolysis technology in the application of wastewater treatment engineering are gradually highlighted. The raw materials used by the traditional micro-electrolysis technology are mainly scrap iron and charcoal, such as early unitary or binary micro-electrolysis filler, the scrap iron and the charcoal are in physical contact, and the filler is easy to passivate and harden in the use process to generate an isolation layer to lose effect, so that the filler is frequently replaced, the workload is high, the cost is high, and the treatment effect and the treatment efficiency are influenced. The invention patent with the patent number of CN101838034A discloses a high-efficiency and anti-hardening micro-electrolysis material and a preparation method thereof, and a high-temperature pore-forming technology is adopted to increase the porosity and the specific surface area of a filler, so that the filler treatment effect is improved and the service life is prolonged. However, in the method, the consumption of iron is fast, the bentonite with higher specific gravity is added, the bentonite is not consumed in the reaction process, so that the amount of sludge generated is larger, and after the iron on the surface of the filler is consumed, the iron inside is surrounded by the clay, so that the reaction effect begins to be reduced.
Therefore, in order to improve the treatment efficiency of the micro-electrolysis filler on the wastewater, one or more metals or non-metals are added on the basis of the binary micro-electrolysis filler to form the multi-element micro-electrolysis filler. The reduction reaction is strengthened by adding another metal to the iron surface to form bimetal, the substance is still the electrochemical corrosion reaction of iron, meanwhile, the added metal with the standard electrode potential higher than that of iron is used as cathode metal to form galvanic couple with iron, and the galvanic couple plays a role in catalyzing and reducing pollutants, wherein the reaction of losing electrons of zero-valent iron in the acidic wastewater is the reaction basis of the whole system, the pollutants can be reduced by obtaining electrons on the surface of the zero-valent iron, and can also be reduced by obtaining electrons on the surface of the bimetal cathode, and the reduction ratio between the two is different along with the difference of reaction pollutants and reaction conditions. At present, reported ternary micro-electrolysis filler systems comprise Co-Fe-C, Cu-Fe-C, Ni-Fe-C, Al-Fe-C and the like, but the current theoretical research is still in the initial stage, because different cathode metals have different standard oxidation potentials and different surface properties, the treatment effect difference among the filler systems is obvious, the reduction efficiency of the same filler system to different pollutants is greatly different, and part of reasons can be due to the difference of the structures and reaction paths of the pollutants.
In addition, the reduction efficiency is influenced to a certain extent by the manner of covering the surface of the cathode metal with the zero-valent iron, the mass ratio of the cathode to the anode, and the like.
The invention patent with the patent number of CN107199037A discloses a preparation method of a Cu/Fe bimetallic material surface modified ozone catalyst, which mainly uses a chemical plating method to plate a small amount of copper on the surface of a steel material to form an incompletely covered simple substance copper film, and forms a passive film on the surface of a bimetal in an acid or neutral solution strong oxidation environment, thereby reducing the loss of the catalyst. The chemical plating method needs to carry out oil and rust removal pretreatment on steel and then uses nitric acid or H2O2The catalyst is an oxidant modified catalyst, the actual operation is complex, the controllability is poor, and the application and the popularization are difficult. Therefore, improving the preparation process of the multi-element iron-carbon micro-electrolysis filler and controlling the cost are key factors for realizing large-scale application and popularization.
Disclosure of Invention
The invention aims to effectively solve the problems of easy hardening and low treatment efficiency of the existing iron-carbon micro-electrolysis filler in wastewater treatment, and provides a preparation method of an iron-based multi-metal alloy micro-electrolysis filler, which comprises the following steps:
(1) and (2) mixing the following components in a mass ratio of 40-60: 7-17, ball-milling iron powder and a plurality of metal catalytic components in horizontal double-rotation stirring ball-milling equipment by a mechanochemical method to obtain iron-based multi-metal alloy powder;
(2) the method comprises the following steps of mixing iron-based multi-metal alloy powder, carbon, clay, a pore-forming agent and the like according to a mass ratio of 47-77: 17-27: 15-25: 0.5-1 proportion and mixing uniformly;
(3) adding water and an adhesive into the uniformly mixed raw materials, kneading the mixture into a cuboid block in a vacuum pug mill, and cutting, granulating and polishing the cuboid block to obtain raw material balls;
(4) and (3) carrying out stepped temperature rise roasting on the obtained raw material balls through a tubular furnace, and sintering in an oxygen-deficient atmosphere to obtain the iron-based multi-metal alloy micro-electrolysis filler.
Firstly, iron powder and a plurality of metal catalytic components are subjected to high-energy ball milling by a mechanochemical method to prepare iron-based multi-metal alloy powder; then, uniformly mixing the raw materials of iron-based multi-metal alloy powder, carbon (preferably sludge carbon), clay, pore-forming agent and the like according to a certain proportion; adding a proper amount of water and a binder into the uniformly mixed raw materials, kneading the raw materials into a cuboid block, cutting and granulating the cuboid block, and polishing the cuboid block to obtain a raw material ball; and finally, placing the raw material balls into a hopper of an automatic feeder of the tubular furnace, continuously passing through a stepped temperature-rising roasting area of the tubular furnace, and continuously sintering the raw material balls in an oxygen-deficient atmosphere to obtain the high-strength iron-based multi-metal alloy micro-electrolysis filler.
Preferably, the iron powder is one or a mixture of two of cast iron powder and reduced iron powder, and the particle size range of the iron powder is 80-200 meshes.
Preferably, the metal catalytic component is one or a mixture of metal powders of copper metal powder, zinc metal powder, nickel metal powder and manganese metal powder, and the particle size range of the metal catalytic component is 120-200 meshes.
Preferably, the charcoal is bamboo charcoal, charcoal or sludge charcoal.
Preferably, the clay is shale, kaolin or attapulgite.
Preferably, the pore-forming agent is sodium carbonate, calcium carbonate or sodium silicate;
preferably, the adhesive is sodium carboxymethyl cellulose or starch.
Preferably, the temperature range of the step-type temperature-rising roasting of the tubular furnace is 1150-1200 ℃, and the roasting time is 1-2 hours.
Preferably, the mass ratio of the iron powder to the metal catalytic component in the step (1) is 45-55: 15-17; when the iron powder is 45-55 powder, the total amount of the metal catalytic components accounts for 13-15 parts by mass. Further preferably, the metal catalytic component is a combination of copper powder and zinc powder, a combination of copper powder and nickel powder or a combination of copper powder and manganese powder, and the mass ratio of the copper powder to other metal powder is 12: 1-3. In the step (2), the iron-based polymetallic alloy powder, the carbon, the clay, the pore-forming agent and other raw materials are mixed according to the mass ratio of 55-65: 20-27: 15-20: 0.5-1.
Most preferably, the mass ratio is 50: 12:3, ball-milling the mixed powder of the iron powder, the copper powder and the zinc powder in a horizontal double-rotation stirring ball-milling device to prepare iron, copper and zinc alloy powder, and then mixing the iron, copper and zinc alloy powder, charcoal, kaolin and sodium silicate according to a ratio of 60: 20: 18: 0.8 mass ratio.
The invention also provides an application of the iron-based polymetallic alloy micro-electrolysis filler, which comprises the following steps:
adding the iron-based polymetallic alloy micro-electrolysis filler into a micro-electrolysis reactor, wherein the filling volume of the filler is 50-75%, adjusting the pH of wastewater inlet water to 3.5-4.8, reacting under the aeration and oxygenation conditions, adjusting the pH of the wastewater outlet water of the micro-electrolysis reactor to 6.8-7.5, and then carrying out precipitation separation.
The application of the invention aims at the treatment of wastewater containing toxic and harmful organic matters and refractory organic matters in industrial wastewater of printing and dyeing, chemical industry and the like, the iron-based polymetallic alloy micro-electrolysis filler is added into a micro-electrolysis reactor, the filling volume of the filler is 50-75%, the pH of wastewater inlet water is adjusted to 3.5-4.8, the wastewater inlet water reacts under the aeration and oxygenation conditions, the filler decomposes organic pollutants in the wastewater through the synergistic action of catalytic reduction and catalytic oxidation, the pH of the wastewater outlet water of the micro-electrolysis reactor is adjusted to 6.8-7.5, and the generated polymetallic hydroxyl complex flocculent sludge enters a biochemical treatment unit or an advanced oxidation unit for further advanced treatment after precipitation and separation.
The invention has the beneficial effects that:
the preparation process of the iron-based multi-metal alloy adopts a mechanochemical method, and strong impact force, strong shearing force, strong friction force and strong extrusion force generated by the relative motion of ball milling media in an inner cylinder body of stirring and ball milling equipment are used for generating strong plastic deformation on the surfaces of different metal powders, generating a series of physicochemical effects of increased specific surface area, partial disordering of crystal structures, lattice distortion, grain size change and the like, realizing the alloying of the metal powders in the high-energy ball milling process, and being beneficial to improving the surface reaction activity and uniformity of the iron-based multi-metal alloy. Therefore, the iron-based multi-metal alloy micro-electrolysis filler prepared by the invention has the advantages of developed porosity, large specific surface area, large current density in acidic wastewater, and uniform distribution of zero-valent iron and catalytic metal components in filler micropores, can effectively prevent the filler from being adhered to each other and further hardened into blocks due to the oxidation of iron powder or the formation of a passive film by the reaction of iron powder and ions in the wastewater, and ensures that the filler keeps the efficient synergistic effect of catalytic reduction and oxidation in the wastewater for a long time.
In addition, the iron-based multi-metal alloy micro-electrolysis filler provided by the invention can form a plurality of micro primary cells by aerating in wastewater, the potential difference of electrodes between catalytic metal components and iron is as high as 1.2V, the generated micro current can excite the wastewater to generate nascent hydrogen and nascent oxygen, and the nascent hydrogen and oxygen have strong reducibility and oxidizability, so that the wastewater can generate strong redox reaction, chromophoric groups or chromophoric groups in the wastewater can be damaged, macromolecular pollutants are broken, and refractory compounds are converted into easily degradable compounds. At the same time, the iron in the filler is consumed by the Fe produced2+Oxidized into Fe in the process of oxygenation and aeration3+，Fe3+The hydrolysate has stronger coagulation adsorption performance, and the ferrous hydroxide and ferric hydroxide colloid generated after adding alkali to adjust the pH after the filler is subjected to micro-electrolysis catalytic reduction can further adsorb COD, ammonia nitrogen and total phosphorus in the wastewaterAnd separating and removing pollutants in the wastewater after flocculation and precipitation.
Compared with the traditional iron-carbon filler, the iron-based multi-metal alloy micro-electrolysis filler has the advantages of high removal efficiency, wide wastewater applicability, long service life and low comprehensive operation cost in wastewater treatment, can be used for pretreatment of industrial wastewater such as printing and dyeing, chemical industry, electroplating, papermaking and the like before a biochemical treatment process, and can also be used in the field of wastewater treatment such as advanced treatment of a sewage treatment plant and the like.
Drawings
FIG. 1 is a flow chart of the preparation of an iron-based multi-metal alloy microelectrolytic filler.
Fig. 2 and 3 are TEM images of an iron-based multi-metal alloy micro-electrolytic filler.
Figure 4 is an XRD pattern of an iron-based multi-metal alloy microelectrolytic filler.
Figure 5 is an EDS spectrum of an iron-based multi-metal alloy microelectrolytic filler.
Detailed Description
Aiming at the problems that the existing iron-carbon micro-electrolysis filler is easy to harden and low in treatment efficiency in wastewater treatment, firstly, iron powder and a plurality of metal catalytic components are subjected to high-energy ball milling by a mechanochemical method to prepare iron-based multi-metal alloy powder; then, uniformly mixing raw materials such as iron-based multi-metal alloy powder, carbon (preferably, sludge carbon), clay, pore-forming agent and the like according to a certain proportion, adding a proper amount of water and a bonding agent to knead the raw materials into a mass, adding a proper amount of water and a bonding agent to knead the mass into a cube in a vacuum pugging machine, cutting and granulating the cube, polishing the cube to obtain a raw material ball, continuously heating the raw material ball to 1150-plus 1200 ℃ through a tube furnace in an anoxic atmosphere, roasting the raw material ball for 1-2 hours, and cooling to obtain the iron-based multi-metal alloy micro-electrolysis filler with higher strength and more porosity, wherein a preparation flow chart of the iron-based multi-metal alloy micro-electrolysis filler is shown in figure 1.
When the wastewater is treated, 50-75% of iron-based multi-metal alloy micro-electrolysis filler is filled in a micro-electrolysis reactor, the pH of inlet water of the wastewater is adjusted to 3.5-4.8, under the aeration and oxygenation conditions, the filler decomposes organic pollutants in the wastewater through the synergistic effect of catalytic reduction and catalytic oxidation, after the pH of outlet water of the micro-electrolysis reactor is adjusted to 6.8-7.5, the generated multi-metal hydroxy complex flocculent sludge is precipitated and then subjected to mud-water separation, and reduction chain scission or oxidation removal of macromolecules and pollutants difficult to degrade in the wastewater is realized.
Example 1:
firstly, mixing a mass ratio of 50: 10, preparing iron-copper alloy powder by high-energy ball milling in horizontal double-rotation stirring ball milling equipment, and then mixing the iron-copper alloy powder, the peat, the shale soil and the sodium carbonate according to a mass ratio of 55: 17: 25: 0.5 weighing the optimized raw materials, putting the raw materials into a double-shaft stirrer, stirring and mixing for 30min, conveying the raw materials to a vacuum pug mill, adding a proper amount of water and sodium carboxymethyl cellulose, kneading the mixture into a cuboid block, cutting and granulating the block, and polishing the block to prepare raw material balls with the particle size of 15 mm. Placing the raw material balls into an automatic feeder of a tube furnace, continuously heating and roasting in a stepped manner through the tube furnace, continuously sintering at the final sintering temperature of 1150 ℃ for about 2 hours in an oxygen-deficient atmosphere to obtain the iron-based multi-metal alloy micro-electrolysis filler with higher strength, and measuring that the specific surface area of the iron-based multi-metal alloy micro-electrolysis filler is 65.6m2/g。
The sewage of a certain printing and dyeing mill is taken as a treatment object, wherein the printing and dyeing wastewater is dark purple, the initial COD is 2156mg/L, and the pH is 7.1. Adding the iron-based polymetallic alloy micro-electrolysis filler into a micro-electrolysis reactor, wherein the filling volume of the filler is 50%, adjusting the pH value of the wastewater to about 4.0, and carrying out air aeration reaction for 1 h. The reaction effluent is light brown, the pH value is increased to 6.2, then the pH value of the effluent is adjusted to about 7.5, dark green ferric hydroxide precipitate is generated, and finally the COD of the supernatant is determined to be 625mg/L, and the removal rate of the COD is 60.8%.
Example 2:
firstly, mixing a mass ratio of 50: 12:3, performing high-energy ball milling on the mixed powder of the iron powder, the copper powder and the zinc powder in a horizontal double-rotation stirring ball milling device to prepare iron, copper and zinc alloy powder, and then mixing the iron, copper and zinc alloy powder, charcoal, kaolin and sodium silicate according to a mass ratio of 60: 20: 18: 0.8 weighing the optimized raw materials, putting the raw materials into a double-shaft stirrer, stirring and mixing for 30min, conveying the raw materials to a vacuum pug mill, adding a proper amount of water and sodium carboxymethyl cellulose, kneading the mixture into a cuboid block, cutting and granulating the block, and polishing the block to prepare the raw material balls with the particle size of 10 mm. And (3) placing the raw material balls into an automatic feeder of a tubular furnace, continuously heating and roasting in a stepped manner through the tubular furnace, wherein the sintering final temperature is 1180 ℃ in an oxygen-deficient atmosphere, the retention time is kept about 1.5 hours, and the raw material balls are continuously sintered to form the iron-based multi-metal alloy micro-electrolysis filler with higher strength.
The sewage of a certain printing and dyeing mill is taken as a treatment object, wherein the printing and dyeing wastewater is dark purple, the initial COD is 3035mg/L, and the pH is 7.3. Adding the iron-based polymetallic alloy micro-electrolysis filler into a micro-electrolysis reactor, wherein the filling volume of the filler is 55 percent, adjusting the pH value of the wastewater to about 3.5, and carrying out air aeration reaction for 1 h. The reaction effluent is mixed with red floccule, the supernatant is colorless after standing, the pH value is increased to 8.3, and finally the COD of the supernatant is measured to be 405mg/L, and the removal rate of the COD is 87%.
Example 3:
firstly, mixing a mass ratio of 40: 12: 2, high-energy ball milling the mixed powder of the iron powder, the copper powder and the nickel powder in a horizontal double-rotation stirring ball milling device to prepare iron, copper and nickel alloy powder, and then mixing the iron, copper and nickel alloy powder, the bamboo charcoal, the attapulgite and the calcium carbonate according to a mass ratio of 60: 25: 22: 0.5 weighing the optimized raw materials, putting the raw materials into a double-shaft stirrer, stirring and mixing for 30min, then conveying the raw materials to a vacuum pug mill, adding a proper amount of water and starch, kneading the mixture into a cuboid block, cutting and granulating the block, and polishing the block to prepare raw material balls with the particle size of 12 mm. And (3) placing the raw material balls into an automatic feeder of a tubular furnace, continuously heating and roasting in a stepped manner through the tubular furnace, keeping the sintering final temperature at 1200 ℃ for about 1h in an oxygen-deficient atmosphere, and continuously sintering to obtain the high-strength iron-based multi-metal alloy micro-electrolysis filler.
The membrane concentrated solution of the wastewater treated by the membrane process is bright yellow, the COD is 145mg/L, and the pH is 7.6. Adding the iron-based polymetallic alloy micro-electrolysis filler into a micro-electrolysis reactor, wherein the filling volume of the filler is 55 percent, adjusting the pH value of the wastewater to about 3.5, and carrying out air aeration reaction for 1 h. The effluent obtained after the reaction is light yellow, the pH value of the effluent is 6.5, the pH value of the effluent is adjusted to about 7.0, a small amount of white precipitate exists, the COD of the effluent is measured to be 44mg/L, and the removal rate of the COD is 70%.
Example 4:
firstly, mixing a mass ratio of 55: 12:1, preparing iron, copper and manganese alloy powder by high-energy ball milling in horizontal double-rotation stirring ball milling equipment, and then mixing the iron, copper and manganese alloy powder, bamboo charcoal, attapulgite and sodium silicate according to a mass ratio of 65: 20: 18: 1, weighing the optimized raw materials, putting the raw materials into a double-shaft stirrer, stirring and mixing for 30min, conveying the raw materials to a vacuum pug mill, adding a proper amount of water and starch, kneading the mixture into a cuboid block, cutting and granulating the block, and polishing the block to prepare raw material balls with the particle size of 18 mm. And (3) placing the raw material balls into an automatic feeder of a tubular furnace, continuously heating and roasting in a stepped manner through the tubular furnace, keeping the sintering final temperature at 1200 ℃ and the retention time at about 1.5h in an oxygen-deficient atmosphere, and continuously sintering to obtain the high-strength iron-based multi-metal alloy micro-electrolysis filler.
The waste water from a certain chemical enterprise plant is taken as a treatment object, and the membrane concentrated solution of the waste water after being treated by the double-membrane process is bright yellow, the COD is 145mg/L, and the pH is 7.6. The combined process of micro-electrolysis filler catalytic reduction and heterogeneous Fenton is adopted, the iron-based polymetallic alloy micro-electrolysis filler is added into a micro-electrolysis reactor, the filling volume of the filler is 55 percent, the pH value of the wastewater is adjusted to be about 3.5, and the air aeration reaction is carried out for 1 hour. The effluent after the reaction is light yellow, the pH of the effluent is 6.5, the effluent after the micro-electrolysis filler catalytic reduction reaction enters a heterogeneous Fenton oxidation unit, the pH of the effluent is adjusted to about 7.0, the effluent is colorless after coagulation and precipitation, the COD of the effluent is 27mg/L, and the removal rate of the COD is 81%.
For further characterization, analysis and examination of the reaction mechanism of the wastewater treatment by the iron-based multi-metal alloy micro-electrolysis filler, the characterization results of the iron-based multi-metal alloy micro-electrolysis filler by using a transmission electron microscope, an X-ray diffractometer and an energy spectrometer are shown in fig. 2, fig. 3, fig. 4 and fig. 5 (the filler prepared in example 2 is used for characterization). Analysis results show that the iron-based multi-metal alloy micro-electrolysis filler has developed porosity and large specific surface area, and zero-valent iron and alloy elements are uniformly distributed in filler micropores, so that the filler can be effectively prevented from being adhered to each other and further hardened into blocks due to the fact that iron powder is oxidized or reacts with ions in wastewater to form a passive film, and the filler can be guaranteed to keep high-efficiency wastewater treatment capacity for a long time.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any person skilled in the relevant art can change or modify the present invention within the scope of the present invention.
Claims (9)
1. The preparation method of the iron-based multi-metal alloy micro-electrolysis filler is characterized by comprising the following steps:
(1) and (2) mixing the following components in a mass ratio of 40-60: 7-17, ball-milling the iron powder and the metal catalytic component in horizontal double-rotation stirring ball-milling equipment by using a mechanochemical method to obtain iron-based multi-metal alloy powder; the metal catalytic component comprises copper powder and zinc powder in a mass ratio of 12: 3;
(2) the preparation method comprises the following steps of (1) mixing iron-based multi-metal alloy powder, carbon, clay and a pore-forming agent according to a mass ratio of 47-77: 17-27: 15-25: 0.5-1 proportion and mixing uniformly;
(3) adding water and an adhesive into the uniformly mixed raw materials, kneading the uniformly mixed raw materials into a cuboid block in a vacuum pug mill, and then cutting, granulating and polishing the cuboid block to generate raw material balls;
(4) the obtained raw material balls are subjected to stepped temperature rise roasting through a tube furnace, and the raw material balls are sintered in an oxygen-deficient atmosphere to obtain the iron-based multi-metal alloy micro-electrolysis filler; the temperature range of the step-type temperature-rising roasting of the tubular furnace is 1150-1200 ℃, and the roasting time is 1-2 hours.
2. The method of claim 1, wherein the iron powder is one or a mixture of two of cast iron powder and reduced iron powder, and the particle size of the iron powder is in the range of 80-200 mesh.
3. The method of claim 1, wherein the metal catalyst component has a particle size of 120 to 200 mesh.
4. The method of claim 1, wherein the charcoal is bamboo charcoal, charcoal or sludge charcoal.
5. The method of claim 1, wherein the clay is shale, kaolin, or attapulgite.
6. The method of claim 1 wherein the pore former is sodium carbonate, calcium carbonate or sodium silicate.
7. The method of claim 1, wherein the binder is sodium carboxymethylcellulose or starch.
8. An iron-based multi-metal alloy micro-electrolysis filler prepared by the preparation method according to any one of claims 1 to 7.
9. Use of an iron-based polymetallic alloy micro-electrolytic filler according to claim 8, characterized in that it comprises the following steps:
adding the iron-based polymetallic alloy micro-electrolysis filler into a micro-electrolysis reactor, wherein the filling volume of the filler is 50-75%, adjusting the pH of wastewater inlet water to 3.5-4.8, reacting under the aeration and oxygenation conditions, adjusting the pH of the wastewater outlet water of the micro-electrolysis reactor to 6.8-7.5, and then carrying out precipitation separation.
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