CN113184945B - Environment-friendly iron-based mineral composite material and preparation method and application thereof - Google Patents
Environment-friendly iron-based mineral composite material and preparation method and application thereof Download PDFInfo
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- 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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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- 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
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention provides a preparation method of an environment-friendly iron-based mineral composite material, which comprises the following steps: A. adding an iron material and a natural mineral into a ball mill, and grinding and mixing uniformly to obtain mixed powder; B. adding the mixed powder into a mixing granulator, mixing and stirring at a low speed, and slowly spraying a binder to the mixed powder to fully contact and mix the binder and the mixed powder to prepare a spherical composite material; C. and (3) putting the spherical composite material into an atmosphere furnace, roasting and hardening at high temperature under the protection of nitrogen, and naturally cooling to obtain the iron-based mineral composite material. The spherical granular iron-based mineral composite material prepared by the invention has stronger adsorption and reduction performances, can ensure the permeability of the spherical iron-based mineral composite material in water, is beneficial to full contact reaction with heavy metal ions in the water, and can realize the removal of various heavy metals in the water. The preparation process of the iron-based mineral composite material is simple and controllable, the cost is low, and the condition of large-scale production is met.
Description
Technical Field
The invention belongs to the technical field of water treatment technology and composite materials, and particularly relates to an environment-friendly iron-based mineral composite material and a preparation method and application thereof.
Background
With the rapid development of the industry in China and the rapid increase of human activities, particularly, the industries such as mining, mineral separation, smelting, electroplating, chemical engineering, leather making, paper making, electronics and the like generate a large amount of waste containing heavy metals and wastewater, and serious pollution is caused to surface water, underground water and the like. At present, the problem of heavy metal pollution of underground water is increasingly prominent, and the prevention and control situation is severe, so that the heavy metal pollution becomes an important concern of ten items of water and ten items of soil.
For the remediation of the water body polluted by the heavy metal, a plurality of challenges still exist in the research and development aspects of efficient, continuous and economic remediation materials at present. In recent years, because iron-based materials have excellent adsorption, precipitation and reduction performances, the repair technology based on iron materials is rapidly developed in the field of polluted water body repair, and different modified nano/particle zero-valent iron, iron oxide, iron composite materials and the like become research hotspots for current heavy metal pollution repair. However, the existing single iron-based material is often limited in the capacity of removing heavy metal pollutants, while the iron-based composite material is mainly synthesized by taking polymetallic, activated carbon and the like as carriers and carrying out chemical reaction with an iron solution, and the preparation process is complex and high in cost, so that the iron-based composite material is difficult to be applied to the restoration of the actual heavy metal polluted groundwater in a large scale.
For example, CN103754952B discloses an iron-based material, which is prepared by sequentially adding a dispersant, a stabilizer, and a collector into a mixture of ferrous salt and ferric salt, and performing a series of complex reactions. CN104174355B discloses a zeolite-supported nano-iron material prepared by placing zeolite particles in FeCl 3 Oscillating in the solution to react until zeolite is saturated to adsorb Fe 3+ By NaBH 4 Reducing the solution, and freeze-drying to obtain the final product. CN 110153157B discloses a porous iron-based adsorption material which is prepared by oxidizing and modifying iron-carbon powder prepared by fluidized roasting through an oxidizing solution, uniformly scattering easily-ionized salts on the surface of the iron-carbon powder, and naturally reacting the easily-ionized salts. CN109821878A discloses a vermiculite supported nano zero-valent iron material which is prepared by loading NaBH in nitrogen environment 4 Dripping the solution into a ferric sulfate solution added with vermiculite, and washing and drying to obtain vermiculite-loaded nano zero-valent iron; the vermiculite disclosed in CN109821878A is loaded with tetraoxideThe ferriferrous material is FeCl 2 And FeCl 3 Dissolving in de-ionized water containing deoxidized gas, adding vermiculite, stirring at a certain temperature, dripping sodium hydroxide solution, heating, stirring, cooling, washing, and drying to obtain the vermiculite-loaded nano ferroferric oxide.
However, most of the iron-based materials are in micron and nanometer powder shapes, so that the spheroidization and large-particle customization of the composite material cannot be realized, the permeability in water is poor, and the recovery treatment after later-stage inactivation is not facilitated. In addition, the preparation method is mainly realized by using various reagents and materials through steps of complex chemical reaction and the like, and high-cost chemical reagents, complicated preparation processes and process parameter limitation are involved in the preparation process, so that the production cost is high, the controllability of each link is poor, the industrialized mass production cannot be realized, and the application of the preparation method in the actual heavy metal polluted water body remediation is limited.
Disclosure of Invention
Aiming at the technical problems, the invention provides an iron-based mineral composite material and a preparation method thereof, aims to provide the iron-based mineral composite material with the advantages of reduction performance, large adsorption capacity, good permeability and environmental friendliness, and aims to provide the preparation method of the iron-based mineral composite material with simple and controllable preparation process, low cost and easy industrial batch production.
The technical scheme adopted by the invention is as follows: the preparation method of the environment-friendly iron-based mineral composite material comprises the following steps:
A. adding an iron material and a natural mineral into a ball mill, and grinding and mixing uniformly to obtain mixed powder;
B. adding the mixed powder into a mixing granulator, firstly mixing and stirring at a low speed, and meanwhile slowly spraying a bonding agent to the mixed powder to ensure that the bonding agent is fully contacted and mixed with the mixed powder, immediately increasing the rotating speed of the granulator after the bonding agent is added, and operating for a certain time to prepare the spherical composite material;
C. and (3) putting the spherical composite material into an atmosphere furnace, roasting and hardening at high temperature in an inert gas environment, and naturally cooling to obtain the iron-based mineral material.
Further, the iron material is zero-valent iron or iron powder particles with the particle size not larger than 4mm, the natural mineral is zeolite or carbonate rock particles with the particle size not larger than 4mm, and the mass ratio of the iron material to the natural mineral is 1:9-1:3.
Furthermore, the ball mill is a vacuum ball milling tank with a teflon lining, and during grinding, the ball mill is firstly vacuumized, and nitrogen is introduced to be used as protective gas for grinding, so that iron materials are prevented from being oxidized.
Furthermore, the binder is 10-20% of sodium alginate or normal silane or polyvinyl alcohol solution by mass, and the addition amount of the binder is 15-18% of the total mass of the mixed powder.
Further, the method for adding the adhesive in the step B comprises the following steps: the adhesive is sprayed onto the mixed powder through a spray head inside the granulator at a rate of 75-100 mL/min per 1kg of the mixed powder at a rotation speed of 100-120 rpm/min of the granulator.
Further, after the adhesive is added, the granulator is operated at the rotating speed of 600-1450 rpm/min for 2-3 min.
Further, the heating temperature of the atmosphere furnace is 200-600 ℃, the heating time is 2-4 h, the inert gas is nitrogen, and the specific steps are as follows: firstly, a vacuum pump is used for vacuumizing the atmosphere furnace to reduce the pressure in the atmosphere furnace to be below 0.04Mpa, then nitrogen is introduced to ensure that the pressure in the atmosphere furnace reaches above 0.02Mpa, and the pressure in the roasting process is kept constant in the range.
The environment-friendly iron-based mineral composite material is composed of zero-valent iron, iron oxide and natural minerals, wherein the valence state of iron in the iron oxide is divalent and trivalent.
Furthermore, the particle size of the iron-based mineral composite material is 2-4 mm, and the iron-based mineral composite material is spherical particles.
The application of the environment-friendly iron-based mineral composite material can be used as a reaction medium of a permeable reaction grid for repairing underground water polluted by heavy metals.
The beneficial effects obtained by the invention are as follows: the iron-based mineral composite material prepared by the invention is of a spherical structure and granular shape, has an average particle size of 2-4 mm, can ensure the permeability of the iron-based mineral composite material in a water body, is beneficial to full contact reaction with heavy metal ions in the water body, and is convenient for later-stage recycling treatment.
1. The iron-based mineral composite material prepared by the invention has stronger adsorption and reduction performance, and can realize various heavy metals such as Pb in water 2+ And Cr 6+ The method has the advantages of high removal efficiency and high reaction rate.
2. The iron-based mineral composite material prepared by the invention is non-toxic and harmless, and does not bring secondary pollution to water bodies.
3. The preparation method of the iron-based mineral composite material provides a customizable preparation process, can be used for manufacturing the iron-based mineral composite materials with different particle sizes according to requirements, can also be used for accurately controlling the content of the iron material in the iron-based mineral composite material and regulating and controlling the adsorption and reduction performance of the material.
4. The preparation process of the iron-based mineral composite material is simple and controllable, has low cost, can be produced in a large scale, and is expected to be widely applied to actual pollution remediation engineering.
5. The iron-based mineral composite material prepared by the invention has high permeability, high adsorption capacity and certain reducibility, and can be used as a reaction medium of a permeable reactive barrier to be applied to groundwater pollution remediation of aquifers with different permeability coefficients.
Drawings
FIG. 1 is a schematic view of a process for preparing an iron-based mineral composite;
FIG. 2 is a graph of a spectrum analysis of the iron-based zeolite prepared in example 1;
FIG. 3 is a graph of a spectrum analysis of the iron-based zeolite prepared in example 2;
FIG. 4 is a Fe element fine narrow scan pattern of X-ray photoelectron spectrum of the iron-based zeolite prepared in example 1;
FIG. 5 shows the iron-based zeolite and Cr prepared in example 1 6+ Fine narrow scanning spectrum of Cr element in the reacted X-ray photoelectron spectrum;
FIG. 6 iron-based carbonate rock prepared in example 4 with Cd 2+ (ii) an X-ray diffraction pattern after the reaction;
figure 7 is a physical representation of the iron-based zeolite prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1: a preparation method of an iron-based mineral composite material, in particular to a preparation method of an iron-based zeolite composite material, which comprises the following steps:
a. respectively adding natural zeolite with the particle size of 1-4 mm and 0.1-1 mu m of zero-valent iron powder into a Teflon vacuum ball milling tank lined in a ball mill according to the mass ratio of 9:1, wherein the volume of the ball milling tank is 500mL, the diameter of a grinding ball is 2-8 mm, the total adding amount of the natural zeolite and the zero-valent iron powder is 50% of the mass of the grinding ball in the ball milling tank, the cover of the ball milling tank is sealed, the ball mill is started after vacuumizing and introducing nitrogen, the rotation speed is set to be 400rpm/min, the revolution speed is 200rpm/min, the grinding time is 2h, and the mixed powder is taken out for standby after grinding;
b. putting mixed powder of natural zeolite and zero-valent iron into a granulation cabin of a mixing granulator, covering and sealing, starting the granulator, spraying an adhesive through a spray head in the granulator under the condition of the rotating speed of 100rpm/min, wherein the adhesive is 15% by mass of a polyvinyl alcohol solution, the adding speed of the adhesive is 75mL/min for every 1kg of mixed powder, and the adding total amount (by mass) of the adhesive is 18% of the total mass of the added mixed powder;
c. after the adhesive is added, the rotating speed of the granulator is increased to 1200rpm/min, the running time is 2min, and a spherical material with the average grain diameter of 2-4 mm is prepared;
d. and (3) putting the spherical material prepared in the last step into an atmosphere furnace, sealing, vacuumizing the furnace by using a vacuum pump to reduce the pressure in the atmosphere furnace to-0.04 Mpa, introducing inert gas to enable the pressure in the furnace to reach 0.02Mpa, repeating the process for three times, and keeping the pressure constant in the range during roasting.
e. Setting the roasting temperature of the atmosphere furnace at 400 ℃, setting the roasting time at 2h, and naturally cooling to obtain the iron-based zeolite composite material, wherein the material is black in color. The average grain diameter of the material is 2-4 mm.
Example 2: a method for preparing an iron-based zeolite composite, which is different from example 1 in that: adding natural zeolite and zero-valent iron powder into a ball milling tank according to the mass ratio of 4:1, grinding and mixing, wherein the total adding amount (by mass) of the adhesive is 15% of the total adding amount of the mixed powder, and the rest steps are completely the same as those in the example 1, thus finally obtaining the iron-based zeolite composite material. The average grain diameter of the material is 2-4 mm.
Example 3: a method for preparing an iron-based zeolite composite, which is different from example 1 in that: the iron material is common iron powder with the grain diameter of 1-2 mm, the natural zeolite and the iron powder are added into a ball milling tank according to the mass ratio of 9:1 for grinding and mixing, and the rest steps are completely the same as the steps in the embodiment 1, so that the iron-based zeolite composite material is finally prepared. The average grain diameter of the material is 2-4 mm.
Example 4: the preparation method of the iron-based carbonate rock composite material is different from that of the embodiment 1 in that: the same particle size carbonate rock was used instead of zeolite as the natural mineral mixed with zero-valent iron, and the rest of the procedure was exactly the same as in example 1. Finally, the iron-based carbonate rock composite material is prepared, and the average grain size of the material is 2-4 mm.
Example 5: a method for preparing an iron-based carbonate rock composite material, which is different from the method of example 4 in that: the iron material is common iron powder with the grain diameter of 1-2 mm, the carbonate rock and the iron powder are added into a ball milling tank according to the mass ratio of 9:1 for grinding and mixing, and the rest steps are completely the same as the steps in the embodiment 4. Finally, the iron-based carbonate rock composite material is prepared, and the average grain size of the material is 2-4 mm.
FIG. 2 is a graph of a spectrum analysis of the iron-based zeolite prepared in example 1; as can be seen from fig. 2, compared with the natural zeolite, the peak of Fe element appears in the energy spectrum analysis chart of the iron-based zeolite, and the Fe content is increased significantly (the Fe atomic percentage is increased to 4.85%), indicating that the iron loading is realized in the iron-based zeolite.
FIG. 3 is a graph of a spectrum analysis of the iron-based zeolite prepared in example 2; as can be seen from fig. 3, compared to the iron-based zeolite prepared in example 1, the iron-based zeolite prepared in example 2 has a significantly increased peak value of Fe element and a significantly increased Fe content (Fe atomic percent increased to 11.94%) due to the increased mass ratio of zero-valent iron added (increased from 10% to 20%).
FIG. 4 is an X-ray photoelectron spectrum of the Fe element fine narrow scan of the Fe-based zeolite prepared in example 1, which can quantitatively characterize the chemical existence form of the Fe element on the surface of the prepared Fe-based zeolite; as can be seen from fig. 4, the surface iron element in the iron-based zeolite is mainly present as ferrous iron and ferric iron. The XPS can only test and analyze the valence and the content of elements within 10nm of the depth of the surface of a sample, so the XPS reflects the chemical state existing form of iron on the surface of the iron-based zeolite. In addition, studies have confirmed that, since zero-valent iron is very easily oxidized, fe @ Fe is generally present in the air atmosphere 2 O 3 The iron oxide shell formed on the surface of the core-shell structure can effectively protect the core from zero-valent iron. The existence of zero-valent iron in the inner core of the iron-based zeolite and divalent iron on the surface of the iron-based zeolite ensures that the iron-based zeolite has certain reducibility.
FIG. 5 shows the iron-based zeolite and Cr prepared in example 1 6+ The fine narrow scan spectrum of Cr element in the X-ray photoelectron spectrum after reaction can be seen from FIG. 5, where Cr is 6+ After reaction, cr is mainly formed on the surface of the iron-based zeolite 3+ In the form of a chemical state of Cr 2 The binding energy of p is respectively around 576.6 and 587.1eV, and Cr 2 O 3 And Cr (OH) 3 The binding energy of (2) is similar, indicating that Cr 6+ Is reduced into Cr by iron 3+ And fixed to the surface of the iron-based zeolite in the form of oxides and hydroxides.
FIG. 6 shows iron-based carbonate rock and Cd prepared in example 4 2+ X-ray diffraction pattern after reaction. Cd in iron-based carbonate rock after reaction is Cd 2+ The oxide and hydroxide exist in forms, which shows that the iron-based carbonate rock can well realize Cd in the solution 2+ Removal and fixation. Removing Fe 0 Outside the characteristic diffraction peak, the diffraction peak is in a certain range,also contains characteristic diffraction peaks of ferrous oxide and ferric oxide, indicating that part of Fe 0 Oxidation and corrosion occur during the reaction process, and iron oxide is generated.
Through X-ray photoelectron spectroscopy diffraction analysis, the valence states of iron in the iron-based mineral composite surface iron oxide prepared in examples 1 to 5 are divalent and trivalent. The iron-based mineral composite materials prepared in examples 1 to 5 had a significantly increased iron content.
Table 1 shows the comparison of the specific surface area and the average pore size before and after ball milling of the natural zeolite, and it can be seen that the specific surface area and the average pore size of the natural zeolite are both significantly increased after ball milling. Through the grinding process of the ball mill, the pore structure of the material can be effectively improved, and the specific surface area is increased.
TABLE 1 surface area before and after ball milling of natural zeolite and average pore diameter
| Test items | Before ball milling | After ball milling |
| Specific surface area (m) 2 /g) | 40.28 | 45.82 |
| Average pore diameter (nm) | 148.95 | 130.94 |
Application example 1: application of iron-based mineral to heavy metal Pb in water body 2+ And Cr 6+ Removal of
Respectively preparing Pb with the concentration of 200mg/L 2+ Aqueous solution and concentration of 5mg/LCr 6+ And (2.5 g) of the iron-based zeolite composite material and the iron-based carbonate rock composite material prepared in the examples 1-5 and 50mL of polluted liquid are respectively added into an erlenmeyer flask according to the solid-to-liquid ratio of 1 2+ And Cr 6+ Comparative test for removal.
Table 2 shows the results of the iron-based mineral composite materials prepared in examples 1 to 5 for heavy metal Pb in water 2+ And Cr 6+ The removal rate of (3). As can be seen from the results of comparative tests, the iron-based mineral composite materials prepared in examples 1 to 5 are used for treating heavy metal Pb in water 2+ And Cr 6+ All with high removal efficiency. Based on the multi-component and multi-element synergistic effect of zeolite and iron, the functions of compounding, surface modification and spheroidization of various materials are achieved by mixing granulation and roasting molding processes under controlled conditions, and the iron-based mineral spherical granular material with obviously increased permeability and reactivity is formed.
TABLE 2 iron-based mineral composite materials for heavy metal Pb in water 2+ And Cr 6+ Removal rate of
| Sample (I) | Pb 2+ Removal Rate (%) | Cr 6+ Removal Rate (%) |
| Example 1 | 95.4 | 93.8 |
| Example 2 | 99.9 | 99.5 |
| Example 3 | 90.1 | 85.7 |
| Example 4 | 99.4 | 93.4 |
| Example 5 | 92.2 | 88.3 |
In the iron-based mineral composite material prepared by the embodiment, the larger the mass proportion of zero-valent iron or iron powder is, the Pb content of the iron-based mineral composite material is 2+ And Cr 6+ The higher the removal rate of (a). Wherein, under the condition that the mass ratio of the zero-valent iron to the iron powder in the composite material is the same, the iron-based mineral composite material prepared by the zero-valent iron has high reactivity to Pb due to the high reaction activity of the zero-valent iron 2+ And Cr 6+ The removal rate of the iron-based mineral is obviously higher than that of an iron-based mineral prepared by iron powder; adding zeolite and carbonate rock into the composite material under the condition of same mass ratio, and synthesizing iron-based composite material by using carbonate rock as raw material for Pb 2+ The removal rate of the catalyst is higher than that of a composite material synthesized by zeolite, and the carbonate rock which is mainly alkaline promotes the precipitation of metal ions; and iron-based composite material synthesized by zeolite to Cr 6+ The removal rate of the catalyst is higher than that of a composite material synthesized by carbonate rock, and the zeolite-rich porous structure is favorable for loading Fe 0 Or Fe 2+ And Cr 6+ The contact is reduced. The particle size of the prepared composite material can be optimally controlled by adjusting the rotating speed of the granulator in the granulation process, so that the material with the required particle size can be obtained. For the selection of the particle size of the reaction medium in the permeable reaction grid, the particle size of 2-4 mm can be ensuredThe reaction performance of the material can be ensured, and the permeability of the material can be ensured.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. The preparation method of the environment-friendly iron-based mineral composite material is characterized by comprising the following steps: the method comprises the following steps:
A. adding an iron material and a natural mineral into a ball mill, and grinding and mixing uniformly to obtain mixed powder;
B. adding the mixed powder into a mixing granulator, firstly mixing and stirring at a low speed, and meanwhile slowly spraying a bonding agent to the mixed powder to ensure that the bonding agent is fully contacted and mixed with the mixed powder, immediately increasing the rotating speed of the granulator after the bonding agent is added, and operating for a certain time to prepare the spherical composite material;
C. putting the spherical composite material into an atmosphere furnace, roasting and hardening at high temperature under an inert gas environment, and naturally cooling to obtain an iron-based mineral composite material;
the iron material is zero-valent iron or iron powder particles with the particle size of not more than 4mm, the natural mineral is zeolite or carbonate rock particles with the particle size of not more than 4mm, and the mass ratio of the iron material to the natural mineral is 1:9-1:3;
the method for adding the adhesive in the step B comprises the following steps: spraying the adhesive on the mixed powder through a spray head inside the granulator at a speed of adding 75-100 mL/min of the adhesive to every 1kg of the mixed powder under the condition that the rotating speed of the granulator is 100-120 rpm/min;
the iron-based mineral composite material is composed of zero-valent iron, iron oxide and natural minerals, wherein the valence state of iron in the iron oxide is divalent and trivalent;
the ball mill is a vacuum ball milling tank with a Teflon lining, and is vacuumized firstly during grinding, and nitrogen is introduced to be used as protective gas for grinding, so that the iron material is prevented from being oxidized.
2. The method for preparing an environment-friendly iron-based mineral composite material according to claim 1, wherein: the adhesive is 10-20% of sodium alginate or normal silane or polyvinyl alcohol solution by mass, and the addition amount of the adhesive is 15-18% of the total mass of the mixed powder.
3. The method for preparing an environment-friendly iron-based mineral composite material according to claim 1, wherein: after the adhesive is added, the granulator is operated at the rotating speed of 600-1450 rpm/min for 2-5 min.
The heating temperature of the atmosphere furnace is 200-600 ℃, and the heating time is 2-4 h; the inert gas is nitrogen, and the method comprises the following specific steps: firstly, a vacuum pump is utilized to vacuumize the atmosphere furnace to reduce the pressure in the atmosphere furnace to be below 0.04MPa, then nitrogen is introduced to ensure that the pressure in the atmosphere furnace reaches above 0.02MPa, and the pressure in the roasting process is kept constant in the range.
4. The environment-friendly iron-based mineral composite material prepared by the preparation method according to claim 1, wherein: the particle size of the iron-based mineral composite material is 2-4 mm, and the iron-based mineral composite material is spherical particles.
5. The use of the environmentally friendly iron-based mineral composite according to claim 4, wherein: the iron-based mineral composite material is used as a reaction medium of a permeable reactive barrier for repairing heavy metal polluted underground water.
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| CN103041812A (en) * | 2012-12-03 | 2013-04-17 | 姜英杰 | Preparation method of catalytic oxidizer for metal pollutants in water |
| CN103769033A (en) * | 2014-01-27 | 2014-05-07 | 北京工业大学 | Preparation method and application of modified zeolite permeable reactive wall filling carrying zero-valent iron powder |
| CN106587369A (en) * | 2016-10-19 | 2017-04-26 | 北京德瑞科森环保科技有限公司 | PRB (permeable reactive barrier) packing for underground water heavy metal pollution, preparation method and application |
| CN111905702A (en) * | 2019-05-10 | 2020-11-10 | 核工业理化工程研究院 | Preparation method of porous particle filter material loaded with nano zero-valent iron for adsorbing and removing heavy metals in water |
| CN110498494A (en) * | 2019-08-01 | 2019-11-26 | 武汉理工大学 | A kind of Zero-valent Iron-mineral composite of high reduction activation and preparation method thereof |
| CN111346591A (en) * | 2020-03-20 | 2020-06-30 | 中国科学院过程工程研究所 | Iron-based-bentonite/carbon composite porous material, and preparation method and application thereof |
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