WO2022160836A1

WO2022160836A1 - Porous iron-manganese composite material for efficiently fixing and removing antimony pollution, preparation method therefor and use thereof

Info

Publication number: WO2022160836A1
Application number: PCT/CN2021/127801
Authority: WO
Inventors: 吴平霄; 陈梅青; 党志
Original assignee: 华南理工大学
Priority date: 2021-01-29
Filing date: 2021-10-31
Publication date: 2022-08-04
Also published as: CN112934165B; CN112934165A

Abstract

The present invention belongs to the technical field of adsorption materials, and discloses a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, a preparation method therefor and the use thereof. The method comprises: formulating a permanganate, a manganese salt and a ferric salt into a permanganate solution, a manganese salt solution and a ferric salt solution, respectively; dropwise adding the permanganate solution into the manganese salt solution, and stirring same to obtain a suspension; adding the ferric salt solution into the suspension, and stirring same to obtain a mixed solution; and adjusting the pH value of the mixed solution to 6.5-8.5, subjecting same to an aging treatment, centrifuging same, taking the precipitate, and washing, drying, grinding and sieving same to obtain the porous iron-manganese composite material for efficiently fixing and removing the antimony pollution. The material has the characteristics of being porous, and having a high specific surface area and a stable adsorption; and the material can be used for treating trivalent antimony and pentavalent antimony pollution, and has a high removal rate and a high adsorption capacity. The method of the present invention is simple, and has mild reaction conditions and a low energy consumption.

Description

A porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution, preparation method and application thereof

technical field

The invention belongs to the technical field of adsorption materials, and in particular relates to a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, and a preparation method and application thereof.

Background technique

Natural antimony mainly exists in the form of ore, and the main valence states are Sb(III) and Sb(V). The global antimony reserves are 4-5 million tons, and China's antimony reserves ranks first in the world. As a major producer of antimony, China's output accounts for about 79.6% of the world's total. In recent years, the unreasonable mining of antimony ore and the irregular use of antimony-containing products have led to a sharp rise in the content of antimony in China's soil, water and atmosphere. Among them, the antimony content in the antimony-rich regions such as Hunan, Guizhou and Guangxi far exceeds the background value. The concentration of Sb in mine drainage and flotation industrial wastewater in China is as high as 30 mg·L ^-1 . The investigation found that the concentration of Sb in the adjacent rivers of Dabaoshan copper-iron mine and Daye iron mine was as high as 900 and 52.7 μg/L.

Antimony has received increasing attention due to its toxicity and biological effects. Since antimony can inhibit the growth of microorganisms and affect the activity of soil enzymes, excessive antimony content in soil has a great impact on the growth and quality of crops, and also has potential harm to human health. Exposure to antimony-containing dust in the air can cause respiratory illness in workers. Antimony poisoning can cause headache, dizziness, abdominal pain, constipation, and loss of appetite. Antimony has been listed as a priority pollutant by the US EPA and the European Union. The World Health Organization stipulates that the hygienic standard for antimony in drinking water is 20ug/L. The limit of antimony concentration in China's "Environmental Quality Standard for Surface Water" (GB3838-2002) is 0.005mg/L.

How to develop a material that can efficiently fix trivalent antimony and pentavalent antimony has become one of the focuses of research. Although there is a method for the preparation of iron-manganese composite oxides and its in-situ antimony removal (CN201910961787.0), the iron-manganese composites reported in the literature do not have a porous structure, and the specific surface area of the adsorption material affects the adsorption. Therefore, there is room for further improvement in the removal performance of pentavalent antimony. Moreover, this document does not discuss the removal effect of iron-manganese composites on trivalent antimony. Trivalent antimony is more harmful to the ecosystem and needs more attention.

technical solutions

In order to overcome the deficiencies of the prior art, the purpose of the present invention is to provide a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, and a preparation method and application thereof.

The primary purpose of the present invention is to provide a method for preparing an antimony-contaminated porous iron-manganese composite material. The prepared porous iron-manganese composite material can be used to deal with trivalent antimony and pentavalent antimony pollution, not only the removal rate is fast but also the adsorption capacity is high.

One of the objects of the present invention is to provide a porous iron-manganese composite material prepared by the above preparation method. The porous iron-manganese composite material has the characteristics of rich pore structure, high specific surface area and stability.

Another object of the present invention is to provide the application of the above-mentioned porous iron-manganese composite material. The porous iron-manganese composite material is used to deal with the problem of antimony pollution (trivalent antimony and pentavalent antimony) in the environment.

The object of the present invention is achieved by at least one of the following technical solutions.

The porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the invention is a porous iron-manganese composite material.

The preparation method of the porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the present invention comprises the following steps:

(1) Prepare soluble permanganate, soluble manganese salt and soluble iron salt into permanganate solution, manganese salt solution and iron salt solution respectively;

(2) slowly dropping the permanganate solution described in step (1) into the manganese salt solution, and stirring to obtain a suspension;

(3) slowly adding the iron salt solution to the suspension described in step (2), and stirring to obtain a mixed solution;

(4) Adjusting the pH value of the mixed solution in step (3) to 6.5-8.5, and then performing aging treatment, centrifuging to obtain the precipitate, washing, drying, grinding, and sieving, to obtain the described solution for high-efficiency immobilization and removal of antimony pollution. Porous ferromanganese composites.

Further, the permanganate in step (1) is one or more of potassium permanganate and sodium permanganate; the manganese salt is one or more of manganese chloride, manganese nitrate and manganese sulfate; Described ferric salt is more than one in ferric nitrate, ferric sulfate and ferric chloride; the molar ratio of described permanganate, manganese salt and ferric salt is (1.5-9): (1-6): (2.5-15 ).

Preferably, the permanganate in step (1) is potassium permanganate; the manganese salt is manganese chloride; and the soluble iron salt is ferric chloride.

Preferably, the molar ratio of the permanganate, manganese and iron salt is (3-6):(2-4):(5-10).

Further, the concentration of the permanganate solution in step (1) is 0.015 mol/L-0.090 mol/L; the concentration of the manganese salt solution is 0.010 mol/L-0.060 mol/L; the concentration of the iron salt solution is 0.025 mol/L-0.150 mol/L.

Preferably, the solvents of the permanganate solution, the manganese salt solution and the iron salt solution in step (1) are all deionized water.

Further, the rate of dropping the permanganate solution into the manganese salt solution in step (2) is 0.1-5 mL/min; the stirring treatment time is 1-3 h.

Further, the rate at which the iron salt solution is added to the suspension in step (3) is 5-10ml/min, and the time for the stirring treatment is 1-3h.

Further, the time of the aging treatment in step (4) is 6-18h.

Further, in step (4), the centrifugal speed is 2000-6000 rpm, and the centrifugal time is 10-20 min; the drying temperature is 40-80°C, and the drying time is 18-36 h; The hole size is 100-500 mesh.

Preferably, in step (4), ammonia water is used to adjust the mixed solution to 6.5-8.5.

Further preferably, in step (4), ammonia water is used to adjust the mixed solution to be 7.0-8.0.

Preferably, the washing in step (4) is to wash the precipitate with deionized water, and the number of washings is 3-5 times.

The present invention provides a porous iron-manganese composite material prepared by the above-mentioned preparation method for efficiently fixing and removing antimony pollution.

The porous iron-manganese composite material for efficiently fixing and removing antimony pollution provided by the present invention can be applied to the treatment of heavy metal-containing antimony pollution.

The porous iron-manganese composite material for efficiently fixing and removing antimony pollution of the present invention is a kind of antimony based on the strong oxidizing property of manganese oxide, the strong affinity of iron oxide for antimony and the high adsorption property of high surface area material for pollutants. The porous iron-manganese composite material prepared with high fixing performance can be used to deal with the problem of antimony pollution in the environment.

beneficial effect

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The preparation process of the present invention is simple, the reaction conditions are mild, the energy consumption is low, the yield is high, and the application prospect is broad;

(2) In the preparation method provided by the present invention, the elements in the iron-manganese oxide used are natural constituents, which are characterized by low price, wide sources, and no environmental pollution; the selected reagents are inexpensive and non-toxic.

(3) The porous iron-manganese composite material provided by the present invention for efficient fixation and removal of antimony pollution has developed pores and a large specific surface area, which is conducive to the removal of pollutants;

(4) The porous iron-manganese composite material provided by the present invention for efficient fixation and removal of antimony contamination is effective against Sb(III) Or the removal of Sb(V) has excellent adsorption, with the characteristics of fast adsorption rate and large adsorption capacity.

Description of drawings

Figure 1a and Figure 1b are the SEM image and the EDS image of the porous iron-manganese composite material prepared in Example 1 for efficient fixation and removal of antimony pollution, respectively;

Fig. 2 is the BET diagram of the porous iron-manganese composite material prepared in Example 1;

3 is a SEM image of the porous iron-manganese composite material prepared in Example 2 for efficient fixation and removal of antimony pollution;

4 is a SEM image of the porous iron-manganese composite material prepared in Example 3 for efficient fixation and removal of antimony pollution;

Fig. 5a and Fig. 5b are graphs showing the result of immobilizing antimony on the porous iron-manganese composite material used for high-efficiency immobilization and removal of antimony pollution in Example 4;

6a and 6b are graphs showing the result of fixing antimony on the porous iron-manganese composite material for high-efficiency fixing and removing antimony pollution in Example 5 with initial concentration.

Embodiments of the present invention

The specific implementation of the present invention will be further described below with reference to examples, but the implementation and protection of the present invention are not limited thereto. It should be pointed out that, if there are any processes that are not described in detail below, those skilled in the art can realize or understand them with reference to the prior art. If the reagents or instruments used do not indicate the manufacturer, they are regarded as conventional products that can be purchased in the market.

实施例Example 1 1

A preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution, comprising the following steps:

(1) Accurately weigh 0.045 mol potassium permanganate, 0.030 mol manganese chloride and 0.075 mol ferric chloride, respectively, add them into 1000 mL of deionized water, and dissolve them uniformly to obtain a potassium permanganate solution with a concentration of 0.045 mol/L. , a manganese chloride solution with a concentration of 0.030 mol/L and a ferric chloride solution with a concentration of 0.075 mol/L;

(2) The potassium permanganate solution was added dropwise to the manganese chloride solution at a dropping rate of 1 mL/min, and then stirred for 2 h to obtain a suspension;

(3) Add the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 7.5 mL/min, and stir for 2 h to obtain a mixed solution;

(4) Adjust the pH of the mixture in step (3) to 7.5 with ammonia water, age for 12 h, centrifuge at 4000 rpm for 15 min, remove the supernatant, rinse with deionized water several times, and dry at 60 °C After 24 hours, grinding through a 200-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.

The morphology and specific surface area of the as-prepared porous Fe-Mn composites are shown in Figure 1a, Figure 1b, and Figure 2. Fig. 1a is the SEM image, Fig. 1b is the EDS image, and Fig. 2 is the BET image. It can be seen from Figure 1a, Figure 1b and Figure 2 that the obtained iron-manganese composite material has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes, and its specific surface area is large, which is conducive to the pollution of pollutants. remove.

实施例Example 22

(1) Accurately weigh 0.015 mol potassium permanganate, 0.010 mol manganese chloride and 0.025 mol ferric chloride, respectively, add them to 1000 mL of deionized water, and dissolve them uniformly to obtain a potassium permanganate solution with a concentration of 0.015 mol/L. , a manganese chloride solution with a concentration of 0.010 mol/L and a ferric chloride solution with a concentration of 0.025 mol/L;

(2) The potassium permanganate solution was added dropwise to the manganese chloride solution at a rate of 0.1 mL/min, followed by stirring for 1 h to obtain a suspension;

(3) Add the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 5.0 mL/min, and stir for 1 h to obtain a mixed solution;

(4) Adjust the pH of the mixed solution in step (3) to 7.0 with ammonia water, age for 6 h, centrifuge at 2000 rpm for 10 min, remove the supernatant, rinse with deionized water several times, and dry at 40 °C 18h, grinding through a 100-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.

The morphology of the prepared porous iron-manganese composites is shown in Figure 3. It can be seen from Figure 3 that the obtained iron-manganese composite material also has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes.

实施例Example 33

(1) Accurately weigh 0.090 mol potassium permanganate, 0.060 mol manganese chloride and 0.150 mol ferric chloride, respectively, add them into 1000 mL of deionized water, and dissolve them uniformly to obtain a potassium permanganate solution with a concentration of 0.090 mol/L. , a manganese chloride solution with a concentration of 0.060 mol/L and a ferric chloride solution with a concentration of 0.150 mol/L;

(2) The potassium permanganate solution was added dropwise to the manganese chloride solution at a dropping rate of 5 mL/min, and then stirred for 3 h to obtain a suspension;

(3) adding the ferric chloride solution to the suspension obtained in step (2) at a dropping rate of 10 mL/min, and stirring for 3 h to obtain a mixed solution;

(4) Adjust the pH of the mixture in step (3) to 8.0 with ammonia water, age for 18 h, centrifuge at 6000 rpm for 20 min, remove the supernatant, rinse with deionized water several times, and dry at 80 °C 36h, grinding through a 500-mesh sieve to obtain the porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution.

The morphology of the as-prepared porous iron-manganese composites is shown in Figure 4. It can be seen from Figure 4 that the obtained iron-manganese composite material also has a rich pore structure, and the nano-sized particles are uniformly distributed on the stacked flakes.

实施例Example 44

In order to explore the relationship between the effect and time of the prepared porous iron-manganese composites for efficient immobilization and removal of antimony pollution in the treatment of wastewater containing heavy metal antimony pollution. The following uses Sb(III) solution and Sb(V) solution as simulated wastewater for testing.

This test includes:

Accurately weigh a number of 0.005g porous iron-manganese composite materials and place them in 50ml centrifuge tubes, respectively, pipette 25ml of Sb(III) solution or Sb(V) solution with a concentration of 20 mg·L ^-1 into the centrifuge tube, and mix thoroughly. After homogenization, place it on a water bath shaker at 30 ± 1°C and shake it. When the shaking time is 1min, 2.5min, 5min, 8min, 10min, 20min, 30min, 60min, 120min, 240min and 480min, take the solution and filter it through 0.45 μm. film, the concentration of Sb(III) or Sb(V) in the solution was measured by atomic absorption spectrophotometer, and the test results are shown in Fig. 5a and Fig. 5b. Fig. 5a shows the adsorption kinetics curve of Sb(III) by the porous iron-manganese composite material for high-efficiency immobilization and removal of antimony pollution, and Fig. 5b is the adsorption kinetics curve of the porous iron-manganese composite material for high-efficiency immobilization and removal of antimony pollution. Sb(V) adsorption kinetics curve.

It can be seen from Fig. 5a and Fig. 5b that the porous iron-manganese composites for high-efficiency immobilization and removal of antimony contamination reach the adsorption equilibrium for Sb(III) or Sb(V) within 60 minutes and 120 minutes, respectively, and then Sb( The adsorption of Sb(III) or Sb(V) did not change much with time, indicating that the porous iron-manganese composites could rapidly remove Sb(III) or Sb(V), and the equilibrium adsorption amounts were 99.5 and 62.1 mg, respectively. ·g ^-1 .

实施例Example 55

In order to explore the relationship between the effect of the prepared porous iron-manganese composites for high-efficiency immobilization and removal of antimony pollution in the treatment of wastewater containing heavy metal antimony pollution and the concentration of antimony in wastewater. The following uses Sb(III) solution and Sb(V) solution as simulated wastewater for testing.

This test includes:

Accurately weigh multiple 0.005g porous iron-manganese composite materials and place them in 50ml centrifuge tubes, respectively, and pipette 25mL of Sb(III) solutions or Sb(V) solutions with different initial concentrations into the centrifuge tubes (the initial concentration is set to 50 mg). L ^-1 , 100 mg L ^-1 , 150 mg L ^-1 , 200 mg L ^-1 , 300 mg L ^-1 , 400 mg L ^-1 , 500 mg L ^-1 ), mix well and place at 30 ± 1 After shaking on a water bath shaker for 24 h, the supernatant was taken through a 0.45 μm filter, and the concentration of Sb(III) or Sb(V) in the solution was measured by atomic absorption spectrophotometer. The test results are shown in Figure 6a and Figure 6b. Figure 6a shows the isotherm adsorption curve of Sb(III) by the porous iron-manganese composite material for high-efficiency immobilization and removal of antimony contamination; Plot of the adsorption isotherm for Sb(V).

It can be seen from Fig. 6a and Fig. 6b that the maximum adsorption capacity of Sb(III) or Sb(V) by the porous iron-manganese composite for high-efficiency immobilization and removal of antimony pollution is 278.3 and 185.7 mg·g ^-1 , respectively , indicating the high-efficiency adsorption of Sb(III) or Sb(V) by the porous iron-manganese composite material.

The above examples are only preferred embodiments of the present invention, and are only used to explain the present invention, but not to limit the present invention. Changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit of the present invention shall belong to the present invention. the scope of protection of the invention.

Claims

A preparation method of a porous iron-manganese composite material for efficiently fixing and removing antimony pollution is characterized in that, comprising the following steps:

(1) Prepare permanganate, manganese and iron salts into permanganate solution, manganese salt solution and iron salt solution respectively;

(2) dropping the permanganate solution described in step (1) into the manganese salt solution, and stirring to obtain a suspension;

(3) adding the iron salt solution to the suspension described in step (2), and stirring to obtain a mixed solution;

(4) Adjusting the pH value of the mixed solution in step (3) to 6.5-8.5, and then performing aging treatment, centrifuging to obtain the precipitate, washing, drying, grinding, and sieving, to obtain the described solution for high-efficiency immobilization and removal of antimony pollution. Porous ferromanganese composites.
The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the permanganate in step (1) is potassium permanganate and sodium permanganate. more than one; the manganese salt is more than one of manganese chloride, manganese nitrate and manganese sulfate; the iron salt is more than one of ferric nitrate, ferric sulfate and ferric chloride; the permanganate, The molar ratio of manganese salt and iron salt is (1.5-9):(1-6):(2.5-15).
The preparation method of the porous iron-manganese composite material for efficiently fixing and removing antimony pollution according to claim 2, wherein the molar ratio of the permanganate, manganese salt and iron salt is (3-6): (2-4): (5-10).
The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the concentration of the permanganate solution in step (1) is 0.015 mol/L-0.090 mol/L; the concentration of the manganese salt solution is 0.010 mol/L-0.060 mol/L; the concentration of the iron salt solution is 0.025 mol/L-0.150 mol/L.
The method for preparing a porous iron-manganese composite material for high-efficiency fixation and removal of antimony pollution according to claim 1, characterized in that, in step (2), the rate of dropping of the permanganate solution into the manganese salt solution dropwise is 0.1-5 mL/min; the stirring treatment time is 1-3h.
The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the rate at which the iron salt solution is added to the suspension in step (3) is 5-10ml/min, The time of the stirring treatment is 1-3h.
The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the aging treatment time in step (4) is 6-18 hours.
The method for preparing a porous iron-manganese composite material for efficient fixation and removal of antimony pollution according to claim 1, wherein the centrifugation rate in step (4) is 2000-6000rpm, and the centrifugation time is 10-20min; The drying temperature is 40-80° C., and the drying time is 18-36 h; the mesh size of the sieving is 100-500 mesh.
A porous iron-manganese composite material prepared by the preparation method according to any one of claims 1 to 8 and used for high-efficiency fixation and removal of antimony pollution.
Application of the porous iron-manganese composite material for efficiently fixing and removing antimony pollution according to claim 9 in the treatment of heavy metal antimony pollution.