CN117753464A - Preparation method and application of alfalfa and ionic rare earth tailing composite catalyst - Google Patents
Preparation method and application of alfalfa and ionic rare earth tailing composite catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a alfalfa and ionic rare earth tailing composite catalyst. The composite catalyst used in the invention is prepared by mixing alfalfa powder and rare earth tailing powder and then co-pyrolyzing. The composite catalyst not only contains rich nitrogen elements, but also is beneficial to preparing nitrogen-doped biochar materials; meanwhile, the rare earth tailings can provide a large number of active sites for the biochar, so that the performance of the activated persulfate is improved. Experiments prove that the porous structure of the biochar catalyst is favorable for adsorbing pollutant reactants on the surface or in pores of the catalyst, so that the degradation efficiency is further improved, and finally, the efficient removal of the dye in the water body is realized. The composite catalyst has the characteristics of wide application range, high treatment efficiency, strong reusability, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the technical field of advanced oxidation treatment, and particularly relates to a preparation method and application of a alfalfa and ionic rare earth tailing composite catalyst.
Background
The printing and dyeing wastewater is main pollution wastewater formed by textile industry, and accounts for 80% of the wastewater in textile and dyeing industry, and the generation of a large amount of printing and dyeing wastewater can cause serious pollution to water body and other environments, even directly endanger human health (carcinogenicity, teratogenicity and mutagenicity, and is called as 'three-induced nature' for short), and most of printing and dyeing wastewater has higher chromaticity, poor biodegradability, complex components and high toxicity, so that the traditional treatment method (such as adsorption method, biochemical method and the like) has poor effect. In order to realize the decolorization and mineralization of the dye in the wastewater, more and more scholars and experts are devoted to searching for a dye wastewater treatment method which is efficient, low in cost, energy-saving and environment-friendly.
In recent years, advanced oxidation technology has been focused on because of advantages such as faster reaction speed, easy control, milder conditions, etc. The advanced oxidation technology utilizes the strong oxidative free radical generated by the reaction system to make water bodyThe organic pollutants in the water are decomposed into micromolecular substances and even mineralized into CO 2 、H 2 O and corresponding inorganic matters thoroughly remove organic pollutants, and the method is one of the main methods for removing toxic and refractory organic pollutants. Of interest, are sulfate radical (SO 4 - However), the persulfate advanced oxidation method has wide pH application range (pH 2-10) and can selectively attack specific electron donating groups and SO 4 - The advantages of high stability, long service life, high oxidation potential, stable chemical property of persulfate, easy transportation and the like are gradually paid great attention to by students in environmental science, material science and the like. However, since persulfates are very stable in nature at room temperature, how to achieve activation of the persulfates has become critical to improving the oxidation performance of the persulfates. At present, in the persulfate activation method, the methods such as heat, ultraviolet light, ultrasonic waves and the like have higher energy consumption and severe reaction conditions; transition metal ion activation requires complex post-treatment (removal of metal ions) to reduce secondary pollution; while alkali activation requires adjustment of the pH of the system (back to neutral pH), too high an alkalinity during the reaction also increases the risk of corrosion to the equipment.
Through preliminary investigation, the biochar becomes a potential efficient green catalyst with the advantages of rich pore structure, large specific surface area, low cost, wide source and the like. The usual waste biomass of wood, sludge, pesticide residues etc. can be formed into biochar by a thermochemical process and used to activate persulfates, thereby producing active species (.OH or SO) 4 - Etc.) to degrade organic contaminants. However, the inventors of the present application found in previous studies that: the existing biochar prepared from waste biomass such as wood, sludge, pesticide residues and the like is usually used as an adsorbent for adsorbing organic pollutants in water, the thorough removal of the organic pollutants is not realized, and the problems of complex subsequent recovery treatment, complicated steps and the like exist; in addition, even if the catalyst is used as a catalyst for activating persulfate, the problems of poor activation effect, large catalyst consumption, long treatment time, low dye removal rate in water body and the like exist, and the aim of efficiently degrading the dye in the water body is difficult to achieve.
Based on the method, the composite catalyst with high graphitization degree, ordered whole structure, rich pore structure, large specific surface area and excellent catalytic activity is prepared from raw materials (alfalfa) with wide sources and low cost, and has important environmental significance and social effect on effectively activating persulfate and realizing efficient degradation of dye.
Disclosure of Invention
In view of the above-mentioned shortcomings, the invention aims to overcome the shortcomings of the prior art, and provides a method for preparing a composite catalyst (raw materials are alfalfa and ionic rare earth tailings and adopting a co-pyrolysis mode) with wide application range, high treatment efficiency and strong recycling property and utilizing the composite catalyst to activate persulfate to degrade dye wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a alfalfa and ionic rare earth tailing composite catalyst, which comprises the following steps:
the composite catalyst is prepared by modifying alfalfa biochar with ionic rare earth tailings.
Further, the composite catalyst is prepared by the following method:
and mixing alfalfa powder and ionic rare earth tailing powder, performing co-pyrolysis, naturally cooling to room temperature, and sieving to obtain the composite catalyst.
Further, the grain sizes of the alfalfa powder and the ionic rare earth tailing powder are 0.1-0.15mm; the mass ratio of the alfalfa powder to the ionic rare earth tailing powder is 1:1-4:1; the co-pyrolysis is carried out under the nitrogen atmosphere, the co-pyrolysis temperature is 600-900 ℃, the heating rate is 5-15 ℃/min, and the constant temperature is kept for 1-4h after the specified temperature is reached.
The invention also discloses a composite catalyst prepared by any one of the preparation methods.
The invention also discloses an application of the composite catalyst in dye wastewater treatment, which comprises the following steps:
mixing the composite catalyst with the dye wastewater, stirring, adding persulfate to carry out degradation reaction for 30-60min, and finishing degradation of the dye in the wastewater.
Further, the addition amount of the composite catalyst is as follows: 0.2-1g of composite catalyst is added into each liter of wastewater.
Further, the initial concentration of the dye wastewater is 0.5-20mg/L.
Further, the dye in the dye wastewater comprises: at least one of rhodamine B, acid orange 7 and methyl orange.
Further, the addition amount of the persulfate is as follows: 1-3mmol of persulfate is added into each liter of wastewater.
Further, the persulfate is potassium hydrogen persulfate or peroxodisulfate.
The invention has the beneficial effects that:
1. the invention provides a method for removing dye in water by activating persulfate through a composite catalyst, which utilizes the persulfate activated by the composite catalyst to degrade dye wastewater, wherein the composite catalyst is prepared by mixing and co-pyrolyzing ion type rare earth tailing powder and alfalfa powder, and the pyrolysis temperature is 600-900 ℃. Compared with the conventional biochar catalyst, the invention selects alfalfa as a precursor of the biochar, and has rich fiber structure. In addition, the alfalfa is taken as leguminous plants, contains rich nitrogen elements, and is favorable for preparing the nitrogen-doped biochar material; the modified substance selected in the experiment is the ionic rare earth tailings, contains rich metal oxides, can provide a large number of active sites for the biochar, improves the performance of activated persulfate, has lower cost (large number) of the ionic rare earth tailings, and solves the potential safety hazard problem of stacking the ionic rare earth tailings. This is an advantage not available with the conventional biochar catalysts. Therefore, the composite catalyst prepared by the invention has abundant porous structure and excellent electron conduction capability, can be beneficial to rapidly adsorbing pollutants (multi-stage pore structure), provides more catalytic active sites for the pollutants, generates an electron transfer process, effectively improves the catalytic activity of organic pollutants such as dye and the like, and finally realizes the efficient removal of the dye in the water body.
2. Compared with other waste biomass such as wood, pesticide residues and the like, the biomass raw material selected by the invention has the addition amount of 0.2-1g of the composite catalyst in per liter of dye wastewater, and has the advantages of less catalyst consumption, high degradation efficiency, short degradation time and the like from the aspects of catalyst usage amount, degradation reaction time and removal rate, and can effectively activate persulfate to realize the purpose of efficiently degrading dye in water.
3. The composite catalyst is a green, environment-friendly and economic catalytic material, and has the advantages of ordered integral structure, rich pore structure, excellent catalytic activity and the like; the preparation raw materials have wide sources and low price, and more accords with the modern scientific and technical standards of environmental protection, high quality and low price; the preparation method has the advantages of simple process, mild reaction condition, lower operation difficulty, green, clean, no secondary pollution and the like, and is suitable for large-scale preparation and convenient for industrialized utilization.
4. The degradation rate of the composite catalyst does not change greatly after the composite catalyst is recycled for 4 times, and the catalyst recovery method after the composite catalyst is used is simpler, and most of the catalyst can be obtained only by suction filtration, so that the composite catalyst has a more stable structure and a simpler recovery mode.
5. The composite catalyst used in the invention can also show higher catalytic activity when degrading dye under the condition of coexistence of a plurality of anions; meanwhile, the catalyst degrades wastewater in the pH value of 3.00-11.00, has higher catalytic activity and has the advantage of wide application range.
Drawings
FIG. 1 is a SEM image of a composite catalyst prepared in example 1 of the present invention, where (a) is ABC-T-600, (b) is ABC-T-700, (c) is ABC-T-800, and (d) is ABC-T-900.
FIG. 2 is an XRD pattern of the composite catalyst (ABC-T-600, ABC-T-700, ABC-T-800, ABC-T-900) prepared in example 1 of the present invention.
FIG. 3 is a graph showing the degradation effect of rhodamine B (RHB) on the composite catalyst prepared under the different pyrolysis temperature conditions in example 1 of the present invention.
FIG. 4 is a graph showing the degradation effect of rhodamine B (RHB) by different proportions of the composite catalyst (ABC-T-800) in the example 2.
FIG. 5 is a graph showing the degradation effect of the composite catalyst (ABC-T-800-4) of example 3 of the present invention on rhodamine B (RHB) under different pH conditions.
FIG. 6 is a graph showing the degradation effect of composite catalyst (ABC-T-800-4) of example 4 of the present invention on rhodamine B (RHB) under different inorganic anion conditions.
Detailed Description
The invention will be further described with reference to the drawings and specific preferred examples, which are not intended to limit the scope of the invention. The materials and instruments used in the examples below are all commercially available.
Example 1:
a preparation method and application of alfalfa and ionic rare earth tailing composite catalyst, in particular to a method for degrading rhodamine B (RHB) by utilizing persulfate activated by the composite catalyst, comprising the following steps:
weighing 50mg of composite catalyst (ABC-T-600, ABC-T-700, ABC-T-800, ABC-T-900) prepared under different pyrolysis conditions, respectively adding the composite catalyst into 50mL of rhodamine B (RHB) solution with the initial pH value of 4.80 and 20mg/L, carrying out shaking table reaction for 40min to ensure that adsorption balance is achieved, then adding 50mg of potassium hydrogen Persulfate (PMS), carrying out degradation reaction for 45min, and completing removal of rhodamine B (RHB) in a water body.
In the embodiment, the adopted composite catalyst (ABC-T-800) is prepared by uniformly mixing ionic rare earth tailings and alfalfa and then pyrolyzing, and comprises the following steps:
(1) Removing impurities: stirring herba Medicaginis in 35 deg.C warm water, centrifuging at 3000r/min, and removing impurities;
(2) And (3) drying: drying the alfalfa subjected to impurity removal in an oven at 60 ℃;
(3) Sieving: respectively sieving dried alfalfa and ionic rare earth tailings with a 0.15mm sieve;
(4) Co-pyrolysis: mixing the prepared alfalfa powder and the ionic rare earth tailing powder according to a ratio of 1:1, performing co-pyrolysis at 800 ℃, naturally cooling to room temperature, and sieving to obtain the composite catalyst.
In this example, the preparation method of the composite catalyst (ABC-T-600) used was substantially the same as that of the composite catalyst (ABC-T-800, i.e., the co-pyrolysis temperature was 800 ℃ C.), except that: the co-pyrolysis temperature for preparing ABC-T-600 is 600 ℃.
In this example, the preparation method of the composite catalyst (ABC-T-700) used was substantially the same as that of the composite catalyst (ABC-T-800, i.e., the co-pyrolysis temperature was 800 ℃ C.), except that: the co-pyrolysis temperature for preparing ABC-T-600 is 700 ℃.
In this example, the preparation method of the composite catalyst (ABC-T-900) is basically the same as that of the composite catalyst (ABC-T-800, i.e. the co-pyrolysis temperature is 800 ℃), and the only difference is that: the co-pyrolysis temperature for preparing ABC-T-600 is 900 ℃.
Characterization of the composite catalysts (ABC-T-600, ABC-T-700, ABC-T-800, ABC-T-900) prepared under different pyrolysis temperature conditions prepared in the examples of the present invention: phase composition XRD, micro morphology SEM.
FIG. 1 is a SEM image of a composite catalyst (ABC-T-600, ABC-T-700, ABC-T-800, ABC-T-900) prepared in example 1 of the present invention. As can be seen from fig. 1, the composite catalyst (ABC-T) contains a distinct porous structure, which provides more catalytically active sites during the subsequent degradation reaction and facilitates the electron transfer process, which is advantageous for improving the catalytic activity of the composite catalyst. In addition, compared with ABC-T-600, ABC-T-700 and ABC-T-900, the porous structure of the ABC-T-800 is richer and more obvious, and the ABC-T-800 can provide more active sites in the degradation catalysis reaction process, so that the influence of different pyrolysis temperatures on degradation catalysis is also shown, and therefore, the selection of a proper pyrolysis temperature is crucial to the efficient removal of dye in a water body.
FIG. 2 is an XRD pattern of the composite catalyst (ABC-T-600, ABC-T-700, ABC-T-800, ABC-T-900) prepared in example 1 of the present invention. As can be seen from FIG. 2, the characteristic peaks of the composite catalyst are compared with SiO 2 The characteristic peak corresponds to the characteristic peak C, i.e. the main non-phase composition is stoneInk carbon and silica. In the degradation reaction process, 1mL of sample is taken by a syringe and placed in a 5mL centrifuge tube (1 mL of methanol quencher is added in advance to terminate the reaction) at 5min, 10min, 15min, 20min and 30min respectively, and then the concentration of the sample is measured at 554nm wavelength by ultraviolet, so that the removal rate of the active persulfate on rhodamine B (RHB) of different composite catalysts is obtained.
FIG. 3 is a graph showing the degradation effect of rhodamine B (RHB) on the composite catalyst prepared under the different pyrolysis temperature conditions in example 1 of the present invention. From fig. 3, it can be seen that the ABC-T composite biochar prepared at 4 pyrolysis temperatures can significantly promote degradation of RHB, and the temperature affects its catalytic activity. When the pyrolysis temperature is lower than 800 ℃, the lower the pyrolysis temperature is found, the lower the catalytic activity of the composite catalyst is. (the degradation efficiency of rhodamine B (RHB) was 94.71%, 90.00% and 63.57% under the catalysis of ABC-T-800, ABC-T-700 and ABC-T-600 at 20min, respectively) but was reduced to 86.34% when the pyrolysis temperature was increased to 900 ℃. On the one hand, too low pyrolysis temperature leads to too low graphitization degree of the composite catalyst, and thus, a rich micropore structure cannot be obtained; on the other hand, the pyrolysis temperature is too high, resulting in the formation of multiple layers of sp 2 The structure reduces the catalytic performance. Therefore, the removal rate of rhodamine B (RHB) is close to 100% by using the composite catalyst (ABC-T-800) prepared by the invention, which also shows that the composite catalyst can efficiently activate PMS and has excellent catalytic performance. From the results, under the conditions that the initial pH value is 4.80, the PMS concentration is 1g/L, the ratio of the ionic rare earth tailings to the alfalfa in the catalyst is 1:1, and the catalyst dosage is 1g/L, ABC-T-800 shows the optimal catalytic performance, and the removal rate of rhodamine B (RHB) is close to 100% within 45 min.
Example 2:
a preparation method and application of alfalfa and ionic rare earth tailing composite catalyst, in particular to a preparation method and application of composite catalyst prepared by utilizing different raw material proportions to activate persulfate to degrade rhodamine B (RHB), comprising the following steps:
under the premise of the pyrolysis temperature of 800 ℃, taking ionic rare earth tailings (uniformly mixed with alfalfa to prepare a composite catalyst through co-pyrolysis, respectively adding the composite catalyst into 50mL of rhodamine B (RHB) solution with the initial pH value of 4.80 and 20mg/L, carrying out shaking table reaction for 40min to ensure that adsorption balance is achieved, then adding 50mg of potassium hydrogen Persulfate (PMS), carrying out degradation reaction for 45min, and completing removal of rhodamine B (RHB) in a water body.
FIG. 4 shows the degradation effect of rhodamine B (RHB) with different proportions. As can be seen from FIG. 4, compared with other ratios, the composite catalyst of the invention has the fastest degradation rate and the best degradation effect when the ratio of alfalfa to the ionic rare earth tailings is 4:1, and can completely degrade rhodamine B (RHB) within 45min under other ratio conditions, namely, the composite catalyst has wide applicable ratio.
Example 3:
a preparation method and application of alfalfa and ionic rare earth tailing composite catalyst, in particular to a method for degrading rhodamine B (RHB) by utilizing persulfate activated by the composite catalyst, comprising the following steps:
taking 5 parts of 50mL and 20mg/L rhodamine B (RHB) solution, respectively adjusting the pH value to 3.00, 5.00, 7.00, 9.00 and 11.00, adding 50mg of the composite catalyst (ABC-T-800-4) prepared in the example 2, reacting for 40min by a shaking table to ensure that adsorption balance is achieved, then adding 50mg of potassium hydrogen Persulfate (PMS), carrying out degradation reaction for 45min, and completing removal of rhodamine B (RHB) in a water body.
In the degradation reaction process, 1mL of sample is taken by a syringe and placed in a 5mL centrifuge tube (1 mL of methanol quencher is added in advance to terminate the reaction) at 5min, 10min, 15min, 20min and 30min respectively, and then the concentration of the sample is measured at 554nm wavelength by ultraviolet, so that the removal rate of the active persulfate on rhodamine B (RHB) of different composite catalysts is obtained.
FIG. 5 is a graph showing the degradation effect of the composite catalyst (ABC-T-800-4) of example 3 of the present invention on rhodamine B (RHB) under different pH conditions. As can be seen from FIG. 5, the ABC-T-800-4 of the present invention has a removal rate of 99.95%,98.68%,99.40%,98.43% and 97.45% for RHB at pH values of 3.00, 5.00, 7.00, 9.00 and 11.00. The pH application range of the whole reaction system is wider, and RHB (more than or equal to 90 percent) can be efficiently removed within 30 minutes from pH=3.00-11.00.
Example 4:
a preparation method and application of alfalfa and ionic rare earth tailing composite catalyst, in particular to a method for degrading rhodamine B (RHB) by utilizing persulfate activated by the composite catalyst, comprising the following steps:
5 parts of 50mL,20mg/L rhodamine B solution (RHB) are taken and 5mmol of HCO is respectively added 3 - 、NO 3 - 、Cl - 、H 2 PO 4 - And after no modification, 50mg of the composite catalyst (ABC-T-800-4) prepared in the example 2 is added, the shaking table reaction is carried out for 40min to ensure that the adsorption balance is achieved, then 50mg of potassium hydrogen Persulfate (PMS) is added, the degradation reaction is carried out for 45min, and the removal of rhodamine B (RHB) in the water body is completed.
In the degradation reaction process, 1mL of sample is taken by a syringe and placed in a 5mL centrifuge tube (1 mL of methanol quencher is added in advance to terminate the reaction) at 5min, 10min, 15min, 20min and 30min respectively, and then the concentration of the sample is measured at 554nm wavelength by ultraviolet, so that the removal rate of the active persulfate on rhodamine B (RHB) of different composite catalysts is obtained.
FIG. 6 is a graph showing the degradation effect of composite catalyst (ABC-T-800-4) of example 4 of the present invention on rhodamine B (RHB) under different inorganic anion conditions. As can be seen from FIG. 6, in NO removal 3 - The effect of the ABC-T-800-4 activated persulfate on degrading rhodamine B solution is not greatly influenced by inorganic anions except inorganic anions, namely the composite catalyst (ABC-T-800-4) has good applicability for most common inorganic anions.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the alfalfa and ionic rare earth tailing composite catalyst comprises the following steps:
the composite catalyst is prepared by modifying alfalfa biochar with ionic rare earth tailings.
2. The method of manufacturing according to claim 1, wherein:
the composite catalyst is prepared by the following steps:
and mixing alfalfa powder and ionic rare earth tailing powder, performing co-pyrolysis, naturally cooling to room temperature, and sieving to obtain the composite catalyst.
3. The preparation method according to claim 2, wherein:
the grain sizes of the alfalfa powder and the ionic rare earth tailing powder are 0.1-0.15mm;
the mass ratio of the alfalfa powder to the ionic rare earth tailing powder is 1:1-4:1;
the co-pyrolysis is carried out under the nitrogen atmosphere, the co-pyrolysis temperature is 600-900 ℃, the heating rate is 5-15 ℃/min, and the constant temperature is kept for 1-4h after the specified temperature is reached.
4. A composite catalyst prepared according to the preparation method of any one of claims 1 to 3.
5. Use of the composite catalyst according to claim 4 in dye wastewater treatment, comprising:
mixing the composite catalyst with the dye wastewater, stirring, adding persulfate to carry out degradation reaction for 30-60min, and finishing degradation of the dye in the wastewater.
6. The use according to claim 5, wherein:
the addition amount of the composite catalyst is as follows: 0.2-1g of composite catalyst is added into each liter of wastewater.
7. The use according to claim 5, wherein:
the initial concentration of the dye wastewater is 0.5-20mg/L.
8. The use according to claim 5, wherein:
the dye in the dye wastewater comprises:
at least one of rhodamine B, acid orange 7 and methyl orange.
9. The use according to claim 5, wherein:
the addition amount of the persulfate is as follows: 1-3mmol of persulfate is added into each liter of wastewater.
10. The use of claim 9, wherein:
the persulfate is potassium hydrogen persulfate or peroxodisulfate.
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