CN111974395A - Red mud-based heterogeneous catalyst, preparation method thereof and pollutant degradation method - Google Patents
Red mud-based heterogeneous catalyst, preparation method thereof and pollutant degradation method Download PDFInfo
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Abstract
The invention discloses a red mud-based heterogeneous catalyst, a preparation method thereof and a pollutant degradation method, belongs to the technical field of heterogeneous catalysts, and solves the problems that a catalyst for degrading organic pollutants in the prior art is high in cost and low in degradation efficiency. The red mud heterogeneous catalyst is prepared by carbonizing red mud and biomass, and the mass ratio of the red mud to the biomass is 5: 1-1: 2. The preparation method comprises the steps of uniformly mixing the red mud and the biomass; and (3) carrying out heating carbonization reaction on the mixture, and sequentially cooling, cleaning and drying reaction products to obtain the red mud heterogeneous catalyst. The degradation method comprises the steps of mixing the red mud heterogeneous catalyst, the organic pollutant aqueous solution and the oxidant, and stirring the mixture for reaction, so that the organic pollutants in the organic pollutant aqueous solution are degraded. The red mud-based heterogeneous catalyst, the preparation method and the pollutant degradation method can be used for degrading organic pollutants.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysts, and particularly relates to a red mud-based heterogeneous catalyst, a preparation method thereof and a pollutant degradation method.
Background
The red mud is strong-alkaline solid waste generated in the alumina industry, 1.0-2.5 tons of red mud can be generated when 1 ton of alumina is produced, and the stockpiling amount of the red mud in China is about 4-8 hundred million tons. The red mud has fine particles and strong alkalinity, contains heavy metals and has great harm to the environment. From the perspective of resources, the red mud contains valuable metals such as iron, aluminum, titanium, rare earth and the like, but the metals have low grade and poor recovery economy, and the development of high-value functional materials has important significance on the comprehensive utilization of the red mud.
By utilizing the physical and chemical properties of the red mud, such as metal element content, large specific surface area and the like, high value-added functional materials such as an adsorbent, a catalyst and the like can be prepared. The red mud is modified to prepare an adsorbent for adsorbing heavy metal ions in wastewater and soil. The strong basicity of the red mud can be used for adsorbing sulfur dioxide in industrial waste gas, and the red mud can also be used as a carrier for loading active components and then adsorbing harmful substances in tail gas. The application of the red mud as a catalyst or a catalyst carrier in biomass pyrolysis for preparing biomass energy has also been widely researched.
The industrial wastewater and the urban wastewater contain a large amount of organic pollutants, the organic pollutants have the characteristics of difficult degradation, high toxicity and the like, which cause great harm to the ecological environment and human health, and active free radicals with strong oxidizing property are generated through the reaction of a catalyst and an oxidant, so that the molecules of the organic pollutants can be effectively degraded. However, the existing catalyst for degrading organic pollutants has high cost and low degradation efficiency.
Disclosure of Invention
In view of the above analysis, the invention aims to provide a red mud-based heterogeneous catalyst, a preparation method thereof and a pollutant degradation method, and solves the problems that the catalyst for degrading organic pollutants in the prior art is high in cost and low in degradation efficiency.
The purpose of the invention is mainly realized by the following technical scheme:
the invention provides a red mud heterogeneous catalyst which is prepared by carbonizing red mud and biomass, wherein the mass content of ferric oxide in the red mud is 10-30%, and the mass ratio of the red mud to the biomass is 5: 1-1: 2.
Further, the biomass is lignocellulosic waste biomass.
Further, the biomass is straw, wood chips, fallen leaves, bagasse, coconut shells and/or livestock manure, and the total mass content of lignin, cellulose and hemicellulose in the biomass exceeds 70%.
The invention also provides a preparation method of the red mud heterogeneous catalyst, which comprises the following steps:
step 1: uniformly mixing the red mud and the biomass to obtain a mixture;
step 2: heating the mixture, and carrying out a carbonization reaction in an inert atmosphere to obtain a reaction product;
and step 3: and cooling, cleaning and drying the reaction product in sequence to obtain the red mud heterogeneous catalyst.
Further, the inert atmosphere is nitrogen or argon, and the inert atmosphere mainly prevents the iron phase reduced in the carbonization process from being oxidized.
Further, in the step 1, the particle size of the red mud is 0.125-0.25 mm, and the particle size of the biomass is 0.125-0.25 mm.
Further, in the step 1, the step of uniformly mixing the red mud and the biomass comprises the following steps: adding the biomass into the red mud for multiple times, and sieving the mixture of the biomass and the red mud after adding the biomass each time to uniformly mix the red mud and the biomass.
Furthermore, the aperture of the sieve is larger than the particle size of the biomass and the particle size of the red mud, so that all the biomass particles and the red mud particles pass through the sieve pores, and the red mud particles and the biomass particles randomly pass through the sieve pores in the sieving process, so that the red mud and the biomass are uniformly mixed.
Further, the mass of biomass per addition gradually decreases.
Further, the step of uniformly mixing the red mud and the biomass comprises the following steps: dividing the biomass into 10 times, wherein the mass of the biomass added each time is 19%, 17%, 15%, 13%, 11%, 9%, 7%, 5%, 3% and 1% of the total mass of the biomass, firstly mixing the red mud and 19% of the biomass, sieving, mixing the undersize mixture and 17% of the biomass, sieving again, and repeating the steps until the biomass is completely added into the red mud.
Further, in the step 2, the heating temperature is 600-1000 ℃, and the heating rate is 5-10 ℃/min.
Further, for hydrogen peroxide or peracetic acid systems, step 2 above includes the steps of:
step 21: heating to 150-250 ℃ at a heating rate of 5-10 ℃/min, heating the mixture for one time, and keeping the temperature for 1-2 hours, wherein an acidic product generated by biomass pyrolysis at this stage can neutralize the alkalinity of the red mud;
step 22: heating to 800-1000 ℃ at a heating rate of 5-10 ℃/min, carrying out secondary heating on the mixture after primary heating, and keeping the temperature for 1-2 h, wherein the biomass is mainly carbonized into porous biochar with a benzene ring structure at the stage, and iron oxide in the red mud is reduced into a low-valence iron phase.
Further, for persulfate systems, the step 2 above comprises the following steps:
and heating to 800-1000 ℃ at a heating rate of 8-10 ℃/min, heating and maintaining the mixture, and keeping the temperature for 2-4 hours, so that more iron oxide in the red mud is reduced into a low-valence iron phase at a high temperature.
Further, in the step 3, the cleaning includes the following steps: and cleaning the cooled reaction product by sequentially adopting a cleaning solvent and deionized water.
Further, the cleaning solvent is one or a mixture of more of methanol, ethanol and acetone in any proportion.
The invention also provides a pollutant degradation method, which comprises the following steps:
step a: mixing a red mud heterogeneous catalyst, an organic pollutant aqueous solution and an oxidant;
step b: and c, stirring the mixture obtained in the step a to react, so that the organic pollutants in the organic pollutant aqueous solution are degraded.
Further, the oxidizing agent is hydrogen peroxide, peroxyacetic acid or persulfate.
Further, the persulfate is ammonium persulfate, potassium persulfate, sodium persulfate, or potassium monopersulfate.
Further, the organic pollutants comprise pesticides, antibiotics, dyes, polychlorinated biphenyl and/or phenolic compounds, and the concentration of the organic pollutants in the organic pollutant aqueous solution is 10-200 mg/L.
Further, the step a includes the steps of: adding the red mud heterogeneous catalyst into an organic pollutant aqueous solution, stirring for 10-60 min, and adding an oxidant into the red mud heterogeneous catalyst and the organic pollutant aqueous solution.
Furthermore, in each liter of organic pollutant water solution, the dosage of the red mud heterogeneous catalyst is 0.5-5 g.
Further, the oxidant is hydrogen peroxide, and the amount of the hydrogen peroxide in each liter of the organic pollutant aqueous solution is 0.02-0.2 mol.
Further, the hydrogen peroxide is added stepwise.
Further, part of the hydrogen peroxide is added to the red mud heterogeneous catalyst and the organic pollutant aqueous solution, and then the rest of the hydrogen peroxide is added to the red mud heterogeneous catalyst and the organic pollutant aqueous solution.
Further, the oxidant is peroxyacetic acid, and the dosage of the peroxyacetic acid in each liter of the organic pollutant aqueous solution is 0.5-5.0 mmol.
Further, peroxyacetic acid was added stepwise.
Further, a part of peroxyacetic acid is added into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, and then the rest hydrogen peroxide is added into the red mud heterogeneous catalyst and the organic pollutant aqueous solution.
Furthermore, the oxidant is persulfate, and the dosage of the persulfate is 0.1-2.0 mmol per liter of the organic pollutant aqueous solution.
Further, in the step b, the stirring reaction time is 20-200 min.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
a) the red mud heterogeneous catalyst provided by the invention is prepared by taking industrial waste residues (red mud) and waste biomass as raw materials through a co-carbonization reaction. Specifically, the ferric ions in the ferric oxide, which is the main component of the red mud, are ferric ions, the catalytic activity of the ferric ions is low, and in the co-carbonization process of the red mud and biomass, the biomass carbonization can reduce part of the ferric ions in the ferric oxide into low-valence ferric ions, so that the catalytic activity of the red mud is improved, and the red mud heterogeneous catalyst is obtained.
b) The red mud heterogeneous catalyst provided by the invention adopts waste materials (red mud and waste biomass) as raw materials, so that the red mud heterogeneous catalyst has the characteristics of low cost, environmental friendliness and the like.
c) According to the preparation method of the red mud heterogeneous catalyst, the biomass is added into the red mud for multiple times, so that the contact probability of the biomass and the red mud can be improved, and the uniform mixing of the biomass and the red mud is promoted.
d) According to the pollutant degradation method provided by the invention, the hydroxyl free radical or the sulfate free radical with strong oxidizing property is generated by the reaction of the low-valent iron in the red mud heterogeneous catalyst and the oxidant, so that the organic pollutants in water are degraded in an oxidizing way, the free radical is nonselective to the degradation of the organic pollutants, the free radical with strong oxidizing property can basically degrade most of the organic pollutants, and the mineralization degree of the organic pollutants is larger.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a scanning electron microscope image of a red mud heterogeneous catalyst prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a red mud heterogeneous catalyst prepared in example 1 of the present invention;
FIG. 3 is a diagram of a degradation ultraviolet-visible spectrum of rhodamine b dye in example 6 of the present invention;
FIG. 4 is a chart of the degraded UV-visible spectrum of methylene blue dye of example 6 of the present invention.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with embodiment 1 of the invention serve to explain the principles of the invention.
The invention provides a red mud heterogeneous catalyst which is prepared by carbonizing red mud and biomass, wherein the mass content of ferric oxide in the red mud is 10-30%, and the mass ratio of the red mud to the biomass is 5: 1-1: 2.
Biomass refers to lignocellulosic waste biomass, such as straw, wood chips, fallen leaves, bagasse, coconut shells, and/or livestock manure, with the total mass content of lignin, cellulose, and hemicellulose in the waste biomass exceeding 70%.
Compared with the prior art, the red mud heterogeneous catalyst provided by the invention is prepared by taking industrial waste residues (red mud) and waste biomass as raw materials through a co-carbonization reaction. Specifically, the ferric ions in the ferric oxide, which is the main component of the red mud, are ferric ions, the catalytic activity of the ferric ions is low, and in the co-carbonization process of the red mud and biomass, the biomass carbonization can reduce part of the ferric ions in the ferric oxide into low-valence ferric ions, so that the catalytic activity of the red mud is improved, and the red mud heterogeneous catalyst is obtained.
Taking the reaction of iron ions with hydrogen peroxide as an example, as shown in the reaction formula, the reaction rate of ferrous ions with hydrogen peroxide is three orders of magnitude higher than that of ferric ions.
Fe2++H2O2→Fe3++OH-+·OH，k＝76M-1S-1
Fe3++H2O2→Fe2++H++·OOH，k＝0.02M-1S-1
In addition, the red mud heterogeneous catalyst adopts waste materials (red mud and waste biomass) as raw materials, so the red mud heterogeneous catalyst has the characteristics of low cost, environmental friendliness and the like.
The invention also provides a preparation method of the red mud heterogeneous catalyst, which comprises the following steps:
step 1: uniformly mixing the red mud and the biomass to obtain a mixture;
step 2: heating the mixture, and performing a carbonization reaction under an inert atmosphere (such as nitrogen or argon) to obtain a reaction product;
and step 3: and cooling, cleaning and drying the reaction product in sequence to obtain the red mud heterogeneous catalyst.
The reaction formula involved in the above preparation method is as follows:
C+Fe2O3→Fe3O4+CO
CO+3Fe2O3→2Fe3O4+CO2
C+Fe3O4→3Fe0+4CO
compared with the prior art, the beneficial effects of the preparation method of the red mud heterogeneous catalyst provided by the invention are basically the same as those of the red mud heterogeneous catalyst, and are not repeated herein.
In order to improve the catalytic activity of the red mud heterogeneous catalyst, in the step 1, the particle size of the red mud is 0.125-0.25 mm, and the particle size of the biomass is 0.125-0.25 mm. The particle size of the red mud and the biomass is too large, the specific surface area of the red mud and the biomass is small, the contact of the red mud and the biomass is reduced, the carbonization reaction is insufficient, and the red mud and the biomass with large particles are used as raw materials, so that the prepared red mud heterogeneous catalyst has relatively small specific surface area and low catalytic activity; the particle size of the red mud and biomass particles is too small, and the particle size of the prepared red mud heterogeneous catalyst is too small, so that the separation and recovery of the red mud heterogeneous catalyst are difficult in the using process. The particle size of the red mud and the biomass is limited within the range, so that the carbonization reaction sufficiency of the red mud and the biomass is further increased and the catalytic activity of the red mud heterogeneous catalyst is improved on the basis of ensuring that the red mud heterogeneous catalyst can be effectively separated and recovered.
In order to realize uniform mixing of the red mud and the biomass, in the step 1, the step of uniformly mixing the red mud and the biomass comprises the following steps: adding the biomass into the red mud for multiple times, and sieving the mixture of the biomass and the red mud after adding the biomass each time to uniformly mix the red mud and the biomass. By adding the biomass into the red mud for multiple times, the contact probability of the biomass and the red mud can be improved, so that the uniform mixing of the biomass and the red mud is promoted.
It should be noted that, after the biomass is added, the mixture of the biomass and the red mud is sieved, and the aperture of the sieve is larger than the particle size of the biomass and the particle size of the red mud, so that all the biomass particles and the red mud particles pass through the sieve pores, and in the sieving process, the red mud particles and the biomass particles randomly pass through the sieve pores, so that the red mud and the biomass are uniformly mixed.
In order to further improve the mixing uniformity of the red mud and the biomass, the mass of the biomass added each time is gradually reduced according to the adding sequence of the biomass. The red mud content in the mixture is high in the initial mixing stage, the biomass can be added to contact with most of the red mud to realize uniform mixing, the mass of the mixture is increased along with the mixing, the red mud content in the mixture is reduced, the adding amount of the biomass in each time is reduced, and the mixing uniformity of the red mud and the biomass can be further improved on the basis of ensuring the mixing efficiency.
Illustratively, the uniformly mixing of the red mud and the biomass comprises the following steps: dividing the biomass into 10 times, wherein the mass of the biomass added each time is 19%, 17%, 15%, 13%, 11%, 9%, 7%, 5%, 3% and 1% of the total mass of the biomass in sequence, firstly, mixing the red mud and 19% of the biomass, adding the mixture into a 60-mesh sieve (with the mesh size of 0.25mm) for primary sieving, mixing the mixture obtained after the primary sieving and 17% of the biomass, adding the mixture into the 60-mesh sieve (with the mesh size of 0.25mm) again for secondary sieving, and repeating the steps until the biomass is completely added into the red mud, thereby obtaining the uniformly mixed mixture of the red mud and the biomass.
In order to control the reaction rate of the carbonization reaction, in the step 2, the heating temperature is 600-1000 ℃, and the heating rate is 5-10 ℃/min.
It should be noted that the red mud heterogeneous catalyst is mainly used for degradation of organic pollutants, and in the degradation process of organic pollutants, the red mud heterogeneous catalyst needs to be matched with hydrogen peroxide, peroxyacetic acid or persulfate to generate radicals, and different carbonization processes need to be performed in step 2 for subsequent applications (hydrogen peroxide or peroxyacetic acid).
Specifically, for a hydrogen peroxide or peracetic acid system, step 2 above includes the steps of:
step 21: heating to 150-250 ℃ at a heating rate of 5-10 ℃/min, heating the mixture for one time, and keeping the temperature for 1-2 hours, wherein an acidic product generated by biomass pyrolysis at this stage can neutralize the alkalinity of the red mud;
step 22: heating to 800-1000 ℃ at a heating rate of 5-10 ℃/min, carrying out secondary heating on the mixture after primary heating, and keeping the temperature for 1-2 h, wherein the biomass is mainly carbonized into porous biochar with a benzene ring structure at the stage, and iron oxide in the red mud is reduced into a low-valent iron phase (ferroferric oxide or zero-valent iron).
For persulfate systems, step 2 above comprises the following steps:
heating to 800-1000 ℃ at a heating rate of 8-10 ℃/min, heating and maintaining the mixture, and keeping the temperature for 2-4 hours, so that more iron oxide in the red mud is reduced into a low-valent iron phase (ferroferric oxide or zero-valent iron) at a high temperature.
In order to remove the biomass pyrolysis products and soluble salts (for example, sodium salts) remained on the surface of the prepared red mud heterogeneous catalyst, in the step 3, the cleaning comprises the following steps: and cleaning the cooled reaction product by sequentially adopting a cleaning solvent and deionized water, wherein the cleaning solvent is one or a mixture of methanol, ethanol and acetone in any proportion.
The invention also provides a pollutant degradation method, which comprises the following steps:
step a: mixing the red mud heterogeneous catalyst, the organic pollutant aqueous solution and an oxidant, wherein the oxidant is one of hydrogen peroxide, peroxyacetic acid and persulfate (such as ammonium persulfate, potassium persulfate, sodium persulfate and potassium monopersulfate);
step b: and c, stirring the mixture obtained in the step a to react, so that the organic pollutants in the organic pollutant aqueous solution are degraded.
Compared with the prior art, the beneficial effects of the pollutant degradation method provided by the invention are basically the same as those of the red mud heterogeneous catalyst, and are not repeated herein.
It should be noted that, in the above pollutant degradation method, the low-valent iron in the red mud heterogeneous catalyst reacts with the oxidant to generate the hydroxyl radical or the sulfate radical with strong oxidizing property, so as to oxidize and degrade the organic pollutant in water, the radical is nonselective for degradation of the organic pollutant, the radical with strong oxidizing property can basically degrade most of the organic pollutant, and the mineralization degree of the organic pollutant is large.
For example, the organic pollutant includes pesticide, antibiotic, dye, polychlorinated biphenyl and/or phenolic compound, and the concentration of the organic pollutant in the aqueous solution of the organic pollutant is 10-200 mg/L.
For the mixing sequence of the red mud heterogeneous catalyst, the aqueous solution of organic pollutants and the oxidant, in particular, the step a comprises the following steps: adding the red mud heterogeneous catalyst into an organic pollutant aqueous solution, stirring for 10-60 min, and adding an oxidant into the red mud heterogeneous catalyst and the organic pollutant aqueous solution. The reason is that the red mud heterogeneous catalyst has a large specific surface area, contains porous biochar, has an adsorption effect on organic pollutants, and can effectively promote the surface catalytic degradation of the organic pollutants through the adsorption effect.
The dosage of the red mud heterogeneous catalyst is specifically 0.5-5 g per liter of organic pollutant aqueous solution. This is because the amount of the red mud heterogeneous catalyst is too small, the catalytic effect is poor, the amount of the red mud heterogeneous catalyst is large, the red mud heterogeneous catalyst consumes part of the active radicals, the catalytic efficiency is also reduced, and the process cost is increased due to the large amount of the red mud heterogeneous catalyst.
Illustratively, the oxidant is hydrogen peroxide, and the amount of the hydrogen peroxide is 0.02-0.2 mol per liter of the organic pollutant aqueous solution. This is because the amount of hydrogen peroxide used is small, the catalytic effect is poor, and the amount of hydrogen peroxide used is large, and the hydrogen peroxide is decomposed into water and oxygen by itself, and the substantial catalytic effect cannot be produced.
In order to further increase the consumption of hydrogen peroxide, the hydrogen peroxide is added step by step, specifically, a part of hydrogen peroxide (for example, 60% of the total mass of hydrogen peroxide) is added into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, and then the rest of hydrogen peroxide is added into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, so that the utilization rate of hydrogen peroxide is increased.
The method is characterized in that the oxidant is peroxyacetic acid, the dosage of the peroxyacetic acid is 0.5-5.0 mmol per liter of the organic pollutant aqueous solution, the dosage of the peroxyacetic acid is small, the catalytic effect is poor, the dosage of the peroxyacetic acid is large, side reactions can occur, and the utilization efficiency of the peroxyacetic acid is low.
Similarly, to increase the peroxyacetic acid utilization rate, the peroxyacetic acid is added in steps, specifically, a part of the peroxyacetic acid (for example, 60% of the total mass of hydrogen peroxide) is added to the red mud heterogeneous catalyst and the organic pollutant aqueous solution, and then the rest of the hydrogen peroxide is added to the red mud heterogeneous catalyst and the organic pollutant aqueous solution, so that the peroxyacetic acid utilization rate is increased.
It should be noted that the oxidizing agent (hydrogen peroxide or peracetic acid) is added step by step, a part of the oxidizing agent (with high concentration and/or large addition amount) is added into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, and then the rest of the hydrogen peroxide (with low concentration and/or small addition amount) is added into the red mud heterogeneous catalyst and the organic pollutant aqueous solution. Because the initial concentration of the organic pollutants in the solution is higher, more oxidants are needed to react to generate active free radicals for oxidative degradation, after the reaction is carried out to a certain degree, the concentration of the organic pollutants is obviously reduced, and then the oxidant with low concentration or small addition is added to fully degrade the residual organic pollutants in the solution. The step-by-step addition of the oxidant can improve the utilization rate of the oxidant and reduce the influence of the residual oxidant in the solution after the reaction on the water quality.
For example, for degrading the same amount of organic pollutants, in the prior art, the amount of the oxidant is required to be 100ml by adopting a one-step adding manner of the oxidant, and only 80ml is required by adopting a step-by-step adding manner of the oxidant of the present invention, and the specific adding manner is as follows: 60 percent (namely 48ml) of the total mass of the oxidant is added into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, and then 40 percent (namely 32ml) of the remaining total mass of the oxidant is added into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, thereby completing the step-by-step addition of the oxidant.
And the oxidant is persulfate, and the dosage of the persulfate is 0.1-2.0 mmol in each liter of organic pollutant aqueous solution. This is because the use amount of persulfate is small, the catalytic effect is poor, and the use amount of persulfate is large, and side reaction occurs, resulting in low persulfate utilization efficiency.
In order to further improve the degradation of organic pollutants, in the step b, the stirring reaction time is 20-200 min. The stirring reaction time is limited in the range, and the stirring reaction time can be properly shortened on the basis of ensuring the full degradation of the organic pollutants, so that the process operation cost can be reduced.
Example 1
The red mud heterogeneous catalyst of the embodiment has a particle size of 0.125mm for red mud and 0.15mm for biomass, and the preparation method of the red mud heterogeneous catalyst comprises the following steps:
step 1: uniformly mixing the red mud and the biomass to obtain a mixture, wherein the mass ratio of the red mud to the biomass is 5: 1;
step 2: heating to 200 ℃ at the heating rate of 5 ℃/min, heating the mixture for one time, and keeping the temperature for 1 h; heating to 1000 ℃ at a heating rate of 10 ℃/min, carrying out secondary heating on the mixture subjected to primary heating, and carrying out heat preservation for 1.5h to obtain a reaction product;
and step 3: and cooling reaction products in sequence, washing by using ethanol and deionized water, and drying to obtain the red mud heterogeneous catalyst. The yield of the catalyst is 83.67%, and the particle size of the catalyst is 0.125-0.15 mm. The catalyst has a large specific surface area and a porous structure (see figure 1), infrared spectroscopic analysis of the catalyst shows that the biochar has rich oxygen-containing functional groups (see figure 2), and the large specific surface area and the oxygen-containing functional groups have a certain promotion effect on the surface adsorption of organic pollutants.
Example 2
The red mud heterogeneous catalyst of the embodiment has a particle size of 0.15mm for red mud and 0.25mm for biomass, and the preparation method of the red mud heterogeneous catalyst comprises the following steps:
step 1: uniformly mixing the red mud and the biomass to obtain a mixture, wherein the mass ratio of the red mud to the biomass is 1: 1;
step 2: heating to 250 ℃ at the heating rate of 10 ℃/min, heating the mixture for the first time, and keeping the temperature for 1.5 h; heating to 800 ℃ at the heating rate of 8 ℃/min, carrying out secondary heating on the mixture subjected to primary heating, and carrying out heat preservation for 2h to obtain a reaction product;
and step 3: and cooling reaction products in sequence, cleaning by adopting methanol and deionized water, and drying to obtain the red mud heterogeneous catalyst. The yield of the catalyst is 67.48%, and the particle size of the catalyst is 0.125-0.15 mm.
Example 3
The red mud heterogeneous catalyst of the embodiment has a particle size of 0.25mm for red mud and 0.125mm for biomass, and the preparation method of the red mud heterogeneous catalyst comprises the following steps:
step 1: uniformly mixing the red mud and the biomass to obtain a mixture, wherein the mass ratio of the red mud to the biomass is 1: 2;
step 2: heating to 150 ℃ at the heating rate of 7 ℃/min, heating the mixture for the first time, and keeping the temperature for 2 hours; heating to 920 ℃ at the heating rate of 5 ℃/min, carrying out secondary heating on the mixture subjected to primary heating, and keeping the temperature for 1h to obtain a reaction product;
and step 3: and cooling reaction products in sequence, washing by using ethanol and deionized water, and drying to obtain the red mud heterogeneous catalyst. The yield of the catalyst is 58.34%, and the particle size of the catalyst is 0.125-0.15 mm.
Example 4
The red mud heterogeneous catalyst of the embodiment has a particle size of 0.23mm for red mud and 0.20mm for biomass, and the preparation method of the red mud heterogeneous catalyst comprises the following steps:
step 1: uniformly mixing the red mud and the biomass to obtain a mixture, wherein the mass ratio of the red mud to the biomass is 3: 1;
step 2: heating to 980 ℃ at the heating rate of 8 ℃/min, heating and maintaining the mixture, and keeping the temperature for 2 hours to obtain a reaction product;
and step 3: and cooling reaction products in sequence, washing by using ethanol and deionized water, and drying to obtain the red mud heterogeneous catalyst. The yield of the catalyst is 81.64%, and the particle size of the catalyst is 0.2-0.23 mm.
Example 5
The red mud heterogeneous catalyst of the embodiment has a particle size of 0.2mm for red mud and 0.15mm for biomass, and the preparation method of the red mud heterogeneous catalyst comprises the following steps:
step 1: uniformly mixing the red mud and the biomass to obtain a mixture, wherein the mass ratio of the red mud to the biomass is 2: 1;
step 2: heating to 800 ℃ at the heating rate of 10 ℃/min, heating and maintaining the mixture, and keeping the temperature for 1h to obtain a reaction product;
and step 3: and cooling reaction products in sequence, washing by using ethanol and deionized water, and drying to obtain the red mud heterogeneous catalyst. The yield of the catalyst is 57.66%, and the particle size of the catalyst is 0.15-0.2 mm.
Example 6
The pollutant degradation method of the embodiment adopts the red mud heterogeneous catalyst of the embodiment 1, and comprises the following steps:
step a: firstly, adding part of hydrogen peroxide into a red mud heterogeneous catalyst and an organic pollutant aqueous solution, and then adding the rest of hydrogen peroxide into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, wherein the dosage of the red mud heterogeneous catalyst is 1g and the dosage of the hydrogen peroxide is 0.05mol per liter of the organic pollutant aqueous solution;
step b: and c, stirring the mixture obtained in the step a for 50min so that the organic pollutants in the organic pollutant aqueous solution are degraded. Wherein, the degradation rate of the acid orange dye (with the concentration of 10mg/L) is 90.46 percent; the degradation rate of the rhodamine b dye (the concentration is 10mg/L) is 98.79 percent; the degradation rate of the methylene blue dye (the concentration is 10mg/L) is 99.77 percent; the total organic carbon removal rate is more than 78.4 percent. The maximum characteristic adsorption peaks of the acid orange, rhodamine b and methylene blue dyes are obviously reduced, and the degradation of dye molecules is shown (see figures 3-4).
Example 7
The pollutant degradation method of the embodiment adopts the red mud heterogeneous catalyst of the embodiment 1, and comprises the following steps:
step a: firstly, adding part of hydrogen peroxide into a red mud heterogeneous catalyst and an organic pollutant aqueous solution, and then adding the rest of hydrogen peroxide into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, wherein in each liter of the organic pollutant aqueous solution, the dosage of the red mud heterogeneous catalyst is 4.5g, and the dosage of the hydrogen peroxide is 0.18 mol;
step b: and c, stirring and reacting the mixture obtained in the step a for 150min, so that the organic pollutants in the organic pollutant aqueous solution are degraded. The degradation rate of tetracycline (with the concentration of 10mg/L) is 89.86 percent, and the degradation rate of carbamazepine (with the concentration of 10mg/L) is 86.54 percent; the degradation rate of the methylene blue dye (with the concentration of 200mg/L) is 86.12%; the total organic carbon removal rate is more than 50.8 percent.
Example 8
The pollutant degradation method of the embodiment adopts the red mud heterogeneous catalyst of the embodiment 2, and comprises the following steps:
step a: firstly, adding part of peroxyacetic acid into a red mud heterogeneous catalyst and an organic pollutant aqueous solution, and then adding the rest hydrogen peroxide into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, wherein in each liter of the organic pollutant aqueous solution, the dosage of the red mud heterogeneous catalyst is 3.2g, and the dosage of the peroxyacetic acid is 0.8 mol;
step b: and c, stirring the mixture obtained in the step a for reaction for 200min, so that the organic pollutants in the organic pollutant aqueous solution are degraded. The degradation rate of tetracycline (with the concentration of 10mg/L) is 87.24%, and the degradation rate of 4-chlorobiphenyl (with the concentration of 10mg/L) is 91.24%; the degradation rate of the rhodamine b dye (the concentration is 40mg/L) is 95.75 percent; the total organic carbon removal rate is more than 65.8 percent.
Example 9
The pollutant degradation method of the embodiment adopts the red mud heterogeneous catalyst of the embodiment 2, and comprises the following steps:
step a: firstly, adding part of peroxyacetic acid into a red mud heterogeneous catalyst and an organic pollutant aqueous solution, and then adding the rest hydrogen peroxide into the red mud heterogeneous catalyst and the organic pollutant aqueous solution, wherein in each liter of the organic pollutant aqueous solution, the dosage of the red mud heterogeneous catalyst is 2.0g, and the dosage of the peroxyacetic acid is 4.5 mol;
step b: and c, stirring the mixture obtained in the step a for 30min so that the organic pollutants in the organic pollutant aqueous solution are degraded. The degradation rate of ofloxacin (the concentration is 20mg/L) is 96.47 percent; the degradation rate of ciprofloxacin (with the concentration of 10mg/L) is 98.47%; the degradation rate of phenol (the concentration is 50mg/L) is 95.44 percent; the degradation rate of tribromophenol (with the concentration of 10mg/L) is 92.15%; the total organic carbon removal rate is greater than 68.34%.
Example 10
The pollutant degradation method of the embodiment adopts the red mud heterogeneous catalyst of the embodiment 5, and comprises the following steps:
step a: mixing a red mud heterogeneous catalyst, an organic pollutant aqueous solution and sodium persulfate, wherein the dosage of the red mud heterogeneous catalyst is 4.1g and the dosage of peracetic acid is 0.2mol in each liter of the organic pollutant aqueous solution;
step b: and c, stirring the mixture obtained in the step a for reaction for 100min, so that the organic pollutants in the organic pollutant aqueous solution are degraded. The degradation rate of methylene blue (the concentration is 80mg/L) is 98.27 percent; the degradation rate of atrazine (the concentration is 10mg/L) is 96.49 percent; the degradation rate of phenol (the concentration is 20mg/L) is 99.34 percent; the total organic carbon removal rate is more than 72.14 percent.
Example 11
The pollutant degradation method of the embodiment adopts the red mud heterogeneous catalyst of the embodiment 5, and comprises the following steps:
step a: mixing a red mud heterogeneous catalyst, an organic pollutant aqueous solution and ammonium persulfate, wherein in each liter of the organic pollutant aqueous solution, the dosage of the red mud heterogeneous catalyst is 3.5g, and the dosage of peroxyacetic acid is 1.6 mol;
step b: and c, stirring and reacting the mixture obtained in the step a for 150min, so that the organic pollutants in the organic pollutant aqueous solution are degraded. The degradation rate of rhodamine b (the concentration is 30mg/L) is 95.77 percent; the degradation rate of carbamazepine (with the concentration of 20mg/L) is 87.99 percent; the degradation rate of 4-chlorobiphenyl (with the concentration of 20mg/L) is 92.67 percent; the total organic carbon removal rate is greater than 62.94%.
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 changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The red mud heterogeneous catalyst is characterized by being prepared by carbonizing reaction of red mud and biomass;
the mass content of ferric oxide in the red mud is 10% -30%, and the mass ratio of the red mud to the biomass is 5: 1-1: 2.
2. A preparation method of a red mud heterogeneous catalyst, which is used for preparing the red mud heterogeneous catalyst of claim 1, and comprises the following steps:
step 1: uniformly mixing the red mud and the biomass to obtain a mixture;
step 2: heating the mixture, and carrying out a carbonization reaction in an inert atmosphere to obtain a reaction product;
and step 3: and cooling, cleaning and drying the reaction product in sequence to obtain the red mud heterogeneous catalyst.
3. The preparation method of the red mud heterogeneous catalyst according to claim 2, wherein in the step 1, the step of uniformly mixing the red mud and the biomass comprises the following steps: adding the biomass into the red mud for multiple times, and sieving the mixture of the biomass and the red mud after adding the biomass each time to uniformly mix the red mud and the biomass.
4. The preparation method of the red mud heterogeneous catalyst according to claim 2, wherein in the step 2, the heating temperature is 600-1000 ℃, and the heating rate is 5-10 ℃/min.
5. The method for preparing the red mud heterogeneous catalyst according to claims 2 to 4, wherein the red mud heterogeneous catalyst is used in combination with hydrogen peroxide or peracetic acid, and the step 2 comprises the following steps:
step 21: heating to 150-250 ℃ at a heating rate of 5-10 ℃/min, heating the mixture for the first time, and keeping the temperature for 1-2 hours;
step 22: heating to 800-1000 ℃ at a heating rate of 5-10 ℃/min, carrying out secondary heating on the mixture after the primary heating, and keeping the temperature for 1-2 h.
6. The preparation method of the red mud heterogeneous catalyst according to claims 2 to 4, wherein the red mud heterogeneous catalyst is used in combination with persulfate, and the step 2 comprises the following steps:
heating to 800-1000 ℃ at a heating rate of 8-10 ℃/min, heating and maintaining the mixture, and keeping the temperature for 2-4 h.
7. A pollutant degradation method, characterized in that the red mud heterogeneous catalyst prepared by the preparation method of any one of claims 2 to 6 is adopted, and the degradation method comprises the following steps:
step a: mixing a red mud heterogeneous catalyst, an organic pollutant aqueous solution and an oxidant;
step b: and c, stirring the mixture obtained in the step a to react, so that the organic pollutants in the organic pollutant aqueous solution are degraded.
8. The pollutant degradation method according to claim 7, characterized in that the amount of the red mud heterogeneous catalyst is 0.5-5 g per liter of the organic pollutant aqueous solution.
9. A pollutant degradation process according to claim 7 or claim 8, in which the oxidising agent is hydrogen peroxide, peroxyacetic acid or a persulfate.
10. A pollutant degradation method according to claim 9, characterised in that the oxidant is hydrogen peroxide, and the amount of hydrogen peroxide used is 0.02-0.2 mol per litre of aqueous solution of organic pollutants;
or the oxidant is peroxyacetic acid, and the dosage of the peroxyacetic acid in each liter of the organic pollutant aqueous solution is 0.5-5.0 mmol;
or the oxidant is persulfate, and the dosage of the persulfate is 0.1-2.0 mmol per liter of the organic pollutant aqueous solution.
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