CN115814789B - Coated Pd-based catalyst, preparation method thereof and method for treating hexavalent chromium in water body - Google Patents
Coated Pd-based catalyst, preparation method thereof and method for treating hexavalent chromium in water body Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to the technical field of industrial wastewater treatment, and discloses a coated Pd-based catalyst, a preparation method thereof and a method for treating hexavalent chromium in water, wherein the preparation method comprises the following steps: (1) Will contain starch and PdCl 2 The pH of the mixed solution of (2) is adjusted to 6.5-7.5, and then it is mixed with MnO 2 Mixing materials to obtain a first solution; (2) Mixing and reacting the first solution with ascorbic acid solution, and then carrying out solid-liquid separation to obtain Pd/MnO 2 A composite material; (3) The Pd/MnO is added to the catalyst 2 Dispersing the composite material and glucose into water, then carrying out polymerization reaction, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a solid product; (4) And in the atmosphere of protective gas, heating the solid product to 550-650 ℃ for calcining to obtain the coated Pd-based catalyst. The coated Pd-based catalyst synthesized by the method has good circulation stability and catalytic activity in the liquid phase catalytic hydrogenation reduction reaction, and can be widely applied to the removal of hexavalent chromium in water.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to a coated Pd-based catalyst, a preparation method thereof and a method for treating hexavalent chromium in water.
Background
In the ecological environment, cr occurs mainly in water and soil in the hexavalent (VI) and trivalent (III) valence states. Although of the same element, the chromium ions in these two valence states have distinct physicochemical properties. Cr (III) tends to exist in cationic form, while Cr (VI) generally exists in oxyanion form, commonly known as CrO 4 2– ，Cr 2 O 2- ，HCrO 4 - The form of presence varies depending on the pH of the environment. Cr (VI) is a highly toxic substance that can be carcinogenic and has mutagenicity, which can cause many health problems. In nature, cr (VI) affects rooting and germination of plants, reproduction and breeding of organisms in soil and marine lifeThe respiratory system of the subject. Cr (VI) has strong fluidity, and can be enriched together after entering human body, so as to damage human organs and cause the problems of liver and kidney injury, lung cancer, skin inflammation, gastrointestinal damage and the like. In contrast, cr (III) is less toxic, less environmentally mobile, and is easily precipitated in water. Thus, the conversion of Cr (VI) to Cr (III) is considered an effective strategy for treating Cr (VI) -containing wastewater.
Currently, commonly used Cr (VI) treatment methods mainly include membrane filtration, electrocoagulation, electrodialysis, photocatalysis, biological treatment, and the like. The methods inevitably have the negative effects of high energy consumption, low efficiency, complex implementation or secondary pollution in application. For example, the membrane filtration method is a pressure-driven separation wastewater treatment technology, and is characterized in that Cr (VI) can be filtered out according to different standards (particle size, concentration, pressure and the like), and the method is easy to operate and has considerable efficiency, but has high cost and complex procedure; the electrocoagulation method has simple process and considerable removal rate, but has high energy consumption and high cost; the electrodialysis method is characterized in that Cr (VI) separation is realized through the selective permeability of an ion exchange membrane under the condition of externally applied current, and the electrodialysis method is easy to control, but has high cost and needs to be replaced; the electrolytic method comprises respectively performing oxidation-reduction reaction on cathode and anode, changing Cr (VI) into valence state, and using OH - Formation of Cr (OH) 3 Insoluble substances are separated, and the method has the advantages of simple operation, stable efficiency, high energy consumption and high cost; the photocatalysis method mainly utilizes free radicals generated by a semiconductor photocatalyst to reduce Cr (VI) under the driving action of light, and has the advantages of environmental friendliness, no secondary pollution, high repeatability, high energy consumption, low sunlight conversion rate and the like; the biological treatment methods (such as biological flocculation, phytoremediation and biological adsorption) have the main advantages of environmental friendliness and no secondary pollution, but have the defects of severe conditions and strong selectivity, and require a subsequent treatment scheme, so that the optimal effect of the biological treatment method can be maximally exerted only in a proper environment. Therefore, the exploration of an efficient and economical method for repairing Cr (VI) containing wastewater is one of the important directions of the current chromium pollution treatment.
The liquid phase catalytic hydrogenation reduction means that a hydrogen source is added into a reaction liquid containing pollutants and a catalyst at normal temperature and normal pressure, the hydrogen source is activated under the action of the catalyst, and the activated hydrogen source further reduces oxidative pollutants, so that the purpose of reducing or removing the toxicity of the pollutants is achieved. The reaction can be carried out at normal temperature and normal pressure, hydrogen is usually used as a reducing agent, and noble metal is used as a catalyst, so that the catalytic hydrogenation technology has the characteristics of simple and convenient device, low energy consumption, high efficiency, no secondary pollution and the like, and can reduce pollutants into low-toxicity or nontoxic substances thoroughly and efficiently, and remove the low-toxicity or nontoxic substances through subsequent treatment. However, the existing noble metal catalyst has poor catalytic activity and stability, thereby limiting the application thereof.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a coated Pd-based catalyst, a preparation method thereof and a method for treating hexavalent chromium in water.
In order to achieve the above object, the present invention provides a method for preparing a coated Pd-based catalyst, comprising the steps of:
(1) Will contain starch and PdCl 2 The pH of the mixed solution of (2) is adjusted to 6.5-7.5, and then it is mixed with MnO 2 Mixing materials to obtain a first solution;
(2) Mixing and reacting the first solution with ascorbic acid solution, and then carrying out solid-liquid separation to obtain Pd/MnO 2 A composite material;
(3) The Pd/MnO is added to the catalyst 2 Dispersing the composite material and glucose into water, then carrying out polymerization reaction, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a solid product;
(4) And in the atmosphere of protective gas, heating the solid product to 550-650 ℃ for calcining to obtain the coated Pd-based catalyst.
Preferably, in step (1), pdCl is present in the first solution 2 With MnO 2 The mass ratio of the materials is 0.1-0.5: 10.
preferably, in step (2), the MnO in the first solution 2 Materials and resistance to damageThe mass ratio of the ascorbic acid in the blood acid solution is 10:0.5 to 1.
Preferably, in the step (2), the ascorbic acid solution contains ascorbic acid, starch and water.
Preferably, in the step (2), the concentration of the ascorbic acid in the ascorbic acid solution is 5-20 mg/mL.
Preferably, in step (3), the Pd/MnO 2 The dosage ratio of the composite material, glucose and water is 0.5g: 0.8-2 g: 20-40 mL.
Preferably, in the step (3), the polymerization temperature is 150-250 ℃ and the polymerization time is 10-15 h in the polymerization reaction process.
Preferably, step (3) comprises: the obtained reaction liquid was filtered, and the obtained solid phase was washed with water until the filtrate was colorless, and then dried to obtain a solid product.
Preferably, in step (4), the shielding gas is N 2 。
Preferably, in step (4), the calcination time is 3 to 6 hours.
Preferably, in the step (4), the temperature rising rate is 4-7 ℃/min.
In a second aspect the present invention provides a coated Pd-based catalyst, the coated Pd-based catalyst being obtainable by a process as described above.
In a third aspect, the present invention provides a method of treating hexavalent chromium in a water body, the method comprising: a body of water containing hexavalent chromium contaminants is treated using a coated Pd-based catalyst as described above.
The invention has the advantages and beneficial effects that:
(1) The synthesized coated Pd-based catalyst has remarkable stability in liquid phase catalytic hydrogenation reduction reaction, so that the catalyst can be recycled, and the carbon coating layer has good hydrophilicity and high isoelectric point, so that the coated Pd-based catalyst has better catalytic performance;
(2) The preparation method provided by the invention is simple, easy to operate, easy to obtain materials, free of secondary pollution and high in feasibility;
(3) The synthesized coated Pd-based catalyst can efficiently remove Cr (VI) in water, does not need any special equipment conditions in the treatment process, can be used for wastewater pretreatment at normal temperature and normal pressure, and has wide application range;
(4) In the method provided by the invention, the coated Pd-based catalyst with good catalytic performance can be prepared by using a small amount of noble metal, and the method has good economic and environmental benefits;
(5) The synthesized coated Pd-based catalyst has good mechanical strength and long service life;
(6) Manganese dioxide (MnO) 2 ) The noble metal Pd is loaded on manganese dioxide and then coated with carbon, is used for reducing Cr (VI) in water, and provides a new material idea and solution for reducing the pollution of the Cr (VI).
Drawings
FIG. 1 is a catalyst Pd/MnO prepared in example 1 of the present invention 2 Scanning electron microscope image at @ C-600;
FIG. 2 is a catalyst Pd/MnO as prepared in comparative example 1 of the present invention 2 Scanning electron microscope images of (2);
FIG. 3 is an XRD pattern of the catalysts prepared in example 1 and comparative examples 1-3 of the present invention;
FIG. 4 is a Raman spectrum of the catalysts prepared in example 1 and comparative examples 1-3 of the present invention;
FIG. 5 shows the Pd/MnO catalyst prepared in example 1 of the present invention 2 A treatment effect diagram of Cr (VI) at different addition amounts of @ C-600;
FIG. 6 shows the catalysts prepared in example 1 and comparative examples 1-3 of the present invention, and MnO 2 A treatment effect map for Cr (VI);
FIG. 7 is a catalyst Pd/MnO prepared in example 1 of the present invention 2 Graph of the reaction at different Cr (VI) initial concentrations @ C-600;
FIG. 8 shows the Pd/MnO catalyst prepared in example 1 of the present invention 2 Graph of the reaction at different pH for @ C-600;
FIG. 9 is a catalyst prepared in example 1 of the present inventionCatalyst Pd/MnO 2 Results of the cyclical stability test at @ C-600;
FIG. 10 is a catalyst Pd/MnO prepared in comparative example 1 of the present invention 2 Is a test result of the cycle stability of (2).
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a preparation method of a coated Pd-based catalyst, which is characterized by comprising the following steps:
(1) Will contain starch and PdCl 2 The pH of the mixed solution of (2) is adjusted to 6.5-7.5, and then it is mixed with MnO 2 Mixing materials to obtain a first solution;
(2) Mixing and reacting the first solution with ascorbic acid solution, and then carrying out solid-liquid separation to obtain Pd/MnO 2 A composite material;
(3) The Pd/MnO is added to the catalyst 2 Dispersing the composite material and glucose into water, then carrying out polymerization reaction, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a solid product;
(4) And in the atmosphere of protective gas, heating the solid product to 550-650 ℃ for calcining to obtain the coated Pd-based catalyst.
In the preparation method provided by the invention, pd/MnO is synthesized by an impregnation method 2 Composite material is then prepared in Pd/MnO by hydrothermal method 2 And coating the surface of the composite material with a carbon layer to obtain the coated Pd-based catalyst.
The invention uses the active component Pd/MnO 2 On one hand, the surface of the catalyst is coated with a carbon layer, so that the poisoning caused by direct contact of active components and pollutants is prevented, and on the other hand, under the action of the carbon coating layer, the loss of active metals is effectively inhibited, so that the coated Pd-based catalyst has high stability and can be reused; meanwhile, the carbon coating layer has better hydrophilicity and high isoelectric point, so that the catalytic activity and the catalytic efficiency of the coated Pd-based catalyst are high.
The invention is not limited to PdCl 2 And MnO 2 The amount of the material to be added may be determined according to the actual situation. In a preferred embodiment, in step (1), pdCl is present in the first solution, from the point of view of cost and catalytic performance 2 With MnO 2 The mass ratio of the materials is 0.1-0.5: 10, the prepared coated Pd-based catalyst has good catalytic performance and low cost. Specifically, in the first solution, pdCl 2 With MnO 2 The mass ratio of materials may be 0.1:10, 0.15:10, 0.18:10, 0.25:10, 0.4:10, or 0.5:10.
In the step (1) of the present invention, the addition of starch facilitates the loading of Pd on MnO 2 On the material. In order to facilitate mixing, in a preferred embodiment, the preparation method of the mixed solution is as follows: pdCl is added to 2 The solution and starch solution are mixed well. As for the concentration and the addition amount of the starch solution, the invention is not limited, and preferably, the concentration of the starch solution is 4-10 g/L, the starch solution and MnO 2 The dosage ratio of the materials is 1-5 mL to 1g.
In step (1) of the present invention, a NaOH solution is used to adjust the pH of the mixed solution. Preferably, the concentration of the NaOH solution is 30-50 g/L.
In a preferred embodiment, in step (2), the MnO in the first solution 2 The mass ratio of the material to the ascorbic acid in the ascorbic acid solution is 10:0.5 to 1, and specifically, for example, may be 10:0.5, 10:0.7, 10:0.8, 10:0.85, 10:0.9 or 10:1.
In a further preferred embodiment, the ascorbic acid solution comprises ascorbic acid, starch and water. It is understood that the ascorbic acid solution may be prepared by directly mixing ascorbic acid, starch and water, or by mixing ascorbic acid, water and starch solution.
In a further preferred embodiment, the concentration of ascorbic acid in the ascorbic acid solution is 5 to 20mg/mL, and specifically, for example, 5mg/mL, 8mg/mL, 10mg/mL, 15mg/mL, 17mg/mL, or 20mg/mL may be used. Since the addition amount of ascorbic acid is small, the present invention calculates the concentration of ascorbic acid in an ascorbic acid solution, and omits the change of the volume of the solution caused by the addition of ascorbic acid.
In a preferred embodiment, step (2) comprises: dropping ascorbic acid solution into the first solution at room temperature under ultrasonic condition, continuing ultrasonic treatment for 0.5-2 h after dropping, then separating solid from liquid, washing, drying, grinding and sieving the obtained solid phase product to obtain Pd/MnO 2 A composite material.
In a preferred embodiment, in step (3), the Pd/MnO 2 The dosage ratio of the composite material, glucose and water is 0.5g: 0.8-2 g: the ratio of 20 to 40mL may be, for example, 0.5g to 1g to 20mL, 0.5g to 1g to 30mL, 0.5g to 1.2g to 25mL, 0.5g to 1.5g to 25mL, 0.5g to 2g to 35mL, or 0.5g to 2g to 40mL.
In a preferred embodiment, the polymerization temperature during the polymerization reaction is 150 to 250 ℃, specifically, for example, 150 ℃, 170 ℃, 200 ℃ or 250 ℃; the polymerization time is 10 to 15 hours, and specifically, for example, may be 10 hours, 12 hours, 14 hours or 15 hours.
In specific implementation, the step (3) includes: the obtained reaction liquid was filtered, and the obtained solid phase was washed with water until the filtrate was colorless, and then dried to obtain a solid product. Preferably, the drying mode is vacuum drying, the drying temperature is 50-70 ℃, and the drying time is 10-14 h.
The present invention is not limited to the specific embodiments of the solid-liquid separation in the step (2) and the step (3), and may be centrifugation, filtration, or the like, and filtration is preferable for the convenience of operation.
The invention also provides a coated Pd-based catalyst, which is prepared by the method.
The invention also provides a method for treating hexavalent chromium in water, which comprises the following steps: a body of water containing hexavalent chromium contaminants is treated using a coated Pd-based catalyst as described above.
In specific implementation, the method for treating hexavalent chromium in the water body comprises the following steps: the coated Pd-based catalyst and formic acid are added into a water body containing hexavalent chromium pollutants to perform a reduction reaction, so that hexavalent chromium in the water body is reduced into trivalent chromium, and the purpose of removing hexavalent chromium is achieved.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto. In the examples below, room temperature refers to 25 ℃.
Example 1
This example is intended to illustrate the preparation of a coated Pd-based catalyst.
(1) 2mL of starch solution (concentration: 6 g/L) and 9mL of PdCl were added 2 The solution (concentration: 2 g/L) was mixed well to obtain a mixed solution, the pH of the mixed solution was adjusted to 7.0 with NaOH solution, and then 1g of MnO was added thereto 2 The materials are mixed evenly by ultrasonic to obtain a first solution, namely, pdCl in the first solution 2 With MnO 2 The mass ratio of the materials is 0.18:10;
(2) Uniformly mixing 80mg of ascorbic acid, 4mL of starch solution (with the concentration of 6 g/L) and 4mL of water to obtain an ascorbic acid solution (namely, the concentration of ascorbic acid in the ascorbic acid solution is 10 mg/mL), dropwise and dispersing the ascorbic acid solution dropwise and dropwise into the first solution under the conditions of room temperature and ultrasound, continuing ultrasound for 1h after the dropwise addition is completed, filtering, washing, drying, grinding and sieving the obtained solid phase product to obtain Pd/MnO 2 A composite material;
(3) 0.5g of the Pd/MnO as described above 2 Adding the composite material and 1g of glucose into 30mL of water, ultrasonically dispersing for 0.5h, transferring the obtained mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, polymerizing for 12h at 200 ℃, cooling the obtained reaction solution to room temperature, filtering, and obtaining the solidWashing the phase with deionized water until the filtrate is colorless, and then drying the phase for 12 hours under the conditions of vacuum and 60 ℃ to obtain a solid product;
(4) Under nitrogen atmosphere, the solid product is heated to 600 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 4 hours to obtain a coated Pd-based catalyst which is named Pd/MnO 2 @C-600。
Example 2
This example is intended to illustrate the preparation of a coated Pd-based catalyst.
(1) 2mL of starch solution (concentration: 6 g/L) and 10mL of PdCl were added 2 The solution (concentration: 2.5 g/L) was mixed well to obtain a mixed solution, the pH of the mixed solution was adjusted to 7.0 with NaOH solution, and then 1g of MnO was added thereto 2 The materials are mixed evenly by ultrasonic to obtain a first solution, namely, pdCl in the first solution 2 With MnO 2 The mass ratio of the materials is 0.25:10;
(2) Uniformly mixing 100mg of ascorbic acid, 6mL of starch solution (with the concentration of 6 g/L) and 4mL of water to obtain an ascorbic acid solution (namely, the concentration of ascorbic acid in the ascorbic acid solution is 10 mg/mL), dropwise and dispersing the ascorbic acid solution dropwise and dropwise into the first solution under the conditions of room temperature and ultrasound, continuing ultrasound for 1h after the dropwise addition is completed, filtering, washing, drying, grinding and sieving the obtained solid phase product to obtain Pd/MnO 2 A composite material;
(3) 0.5g of the Pd/MnO as described above 2 Adding the composite material and 1g of glucose into 25mL of water, performing ultrasonic dispersion for 0.5h, transferring the obtained mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, polymerizing for 11h at 230 ℃, cooling the obtained reaction liquid to room temperature, filtering, washing the obtained solid phase with deionized water until the filtrate is colorless, and then drying for 12h at 60 ℃ under vacuum to obtain a solid product;
(4) Under nitrogen atmosphere, the solid product is heated to 620 ℃ at a heating rate of 6 ℃/min, and the temperature is kept for 3 hours to obtain a coated Pd-based catalyst which is named Pd/MnO 2 @C-620。
Example 3
This example is intended to illustrate the preparation of a coated Pd-based catalyst.
(1) 2mL of starch solution (concentration: 6 g/L) and 10mL of PdCl were added 2 The solution (concentration: 4 g/L) was mixed well to obtain a mixed solution, the pH of the mixed solution was adjusted to 7.2 with NaOH solution, and then 1g of MnO was added thereto 2 The materials are mixed evenly by ultrasonic to obtain a first solution, namely, pdCl in the first solution 2 With MnO 2 The mass ratio of the materials is 0.4:10;
(2) Uniformly mixing 90mg of ascorbic acid, 3mL of starch solution (with the concentration of 6 g/L) and 3mL of water to obtain an ascorbic acid solution (namely, the concentration of ascorbic acid in the ascorbic acid solution is 15 mg/mL), dropwise and dispersing the ascorbic acid solution dropwise and dropwise into the first solution under the conditions of room temperature and ultrasound, continuing ultrasound for 1h after the dropwise addition is completed, filtering, washing, drying, grinding and sieving the obtained solid phase product to obtain Pd/MnO 2 A composite material;
(3) 0.5g of the Pd/MnO as described above 2 Adding the composite material and 1g of glucose into 35mL of water, performing ultrasonic dispersion for 0.5h, transferring the obtained mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, polymerizing for 14h at 180 ℃, cooling the obtained reaction liquid to room temperature, filtering, washing the obtained solid phase with deionized water until the filtrate is colorless, and then drying for 12h at 60 ℃ under vacuum to obtain a solid product;
(4) Under nitrogen atmosphere, the solid product is heated to 590 ℃ at a heating rate of 4 ℃/min, and the temperature is kept for 5 hours to obtain a coated Pd-based catalyst which is named Pd/MnO 2 @C-590。
Comparative example 1
The procedure is carried out as in example 1, except that the catalyst is not present in Pd/MnO 2 The composite material is coated with a carbon layer, and is directly used as a catalyst and is marked as Pd/MnO 2 ；
In particular, catalyst Pd/MnO 2 The preparation method of the (C) comprises the following steps:
(1) 2mL of starch solution (concentration: 6 g/L) and 9mL of PdCl were added 2 Mixing the solutions (concentration of 2 g/L)Homogenizing to obtain a mixed solution, adjusting the pH of the mixed solution to 7.0 with NaOH solution, and adding 1g MnO thereto 2 The materials are mixed evenly by ultrasonic to obtain a first solution, namely, pdCl in the first solution 2 With MnO 2 The mass ratio of the materials is 0.18:10;
(2) Uniformly mixing 80mg of ascorbic acid, 4mL of starch solution (with the concentration of 6 g/L) and 4mL of water to obtain an ascorbic acid solution (namely, the concentration of ascorbic acid in the ascorbic acid solution is 8 mg/mL), dropwise and dispersing and dropwise adding the ascorbic acid solution into the first solution under the conditions of room temperature and ultrasonic, continuing ultrasonic for 1h after the dropwise adding is completed, filtering, washing, drying, grinding and sieving the obtained solid phase product to obtain a catalyst, namely Pd/MnO 2 ；
Comparative example 2
The procedure was carried out as in example 1, except that the calcination temperature was 400℃to give a catalyst, designated Pd/MnO 2 @C-400。
Comparative example 3
The procedure was carried out as in example 1, except that the calcination temperature was 800℃to give a catalyst, designated Pd/MnO 2 @C-800。
Test case
(1) The catalysts prepared in example 1 and comparative example 1 were characterized using a scanning electron microscope, and the results are shown in fig. 1 (example 1) and fig. 2 (comparative example 1).
As can be seen from FIG. 1, the Pd/MnO after coating C 2 The catalyst @ C-600 was observed to be grape-like aggregated particles in a 1000-fold scanning electron microscope, with aggregate cluster sizes varying from 50 to 150 μm.
As can be seen from FIG. 2, pd/MnO without C wrap 2 The surface of the catalyst had irregularly shaped Pd particles with a diameter of about 30. Mu.m.
(2) The catalyst Pd/MnO prepared in example 1 2 The results of the detection at @ C-600 using an inductively coupled plasma emission spectrometer (ICP-OES) showed that the Pd loading in the catalyst was 0.46wt%.
(3) The catalysts prepared in example 1 and comparative examples 1 to 3 were subjected to X-ray diffraction, and the results are shown in FIG. 3.
As can be seen from FIG. 3, mnO 2 、Pd/MnO 2 、Pd/MnO 2 @C-400、Pd/MnO 2 @C-600 and Pd/MnO 2 The catalyst @ C-800 has Pd characteristic diffraction peaks at diffraction angles of 28.8 degrees, 40.5 degrees and 56.7 degrees, and MnO at diffraction angles of 26.7 degrees, 42.9 degrees, 59.8 degrees and 72.3 degrees 2 Is a characteristic diffraction peak of (2).
(4) The catalysts prepared in example 1 and comparative examples 1 to 3 were subjected to Raman spectroscopy (Raman) analysis, and the results are shown in fig. 4.
As can be seen from FIG. 4, in the Raman spectra of the different catalysts, the Pd/MnO of the single metal 2 The catalyst was only at 637cm -1 One peak band was seen, and Pd/MnO 2 @C-400、Pd/MnO 2 @C-600 and Pd/MnO 2 The @ C-800 catalysts were each at 1334cm -1 And 1600cm -1 Two distinct peak bands were seen, namely Pd/MnO respectively 2 The D and G bands of the @ C catalyst, respectively, contributed to the defective sites of C, indicating that C successfully coated the Pd particles in the catalyst.
Application test case
(1) Catalyst Pd/MnO 2 Relation between addition amount of @ C-600 and Cr (VI) treatment effect
The catalyst Pd/MnO prepared in example 1 2 The @ C-600 is used for treating Cr (VI) in a water body, and the method is as follows: adding a catalyst and formic acid into a water body containing Cr (VI) pollutants, regulating the pH value of the water body to 2, and carrying out reduction reaction for 2 hours at normal temperature and normal pressure; wherein the initial concentration of Cr (VI) is 1mM, and the concentration of the catalyst is 0.05g/L, 0.1g/L, 0.15g/L, and 0.25g/L, respectively. The test results are shown in FIG. 5.
As can be seen from FIGS. 5 (a) and 5 (b), the larger the catalyst addition amount, the better the reduction effect on Cr (VI), and when the catalyst addition amount is 0.25g/L, 77% of Cr (VI) in the water body is reduced within 120 min.
(2) Treatment effect of different catalysts on Cr (VI)
The catalysts prepared in example 1, comparative examples 1-3 and MnO (used in example 1) 2 The material is used for treating water bodyCr (VI) is prepared by the following steps: adding a catalyst and formic acid into a water body containing Cr (VI) pollutants, regulating the pH value of the water body to 2, and carrying out reduction reaction for 2 hours at normal temperature and normal pressure; wherein the initial concentration of Cr (VI) is 1mM and the concentration of the catalyst is 0.25g/L. The removal results are shown in FIG. 6.
As can be seen from FIGS. 6 (a) and 6 (b), the catalyst Pd/MnO prepared in comparative example 1 2 The catalyst Pd/MnO prepared in example 1 has the best treatment effect on Cr (VI) 2 @C-600 times, mnO 2 Is the least effective. In addition, the catalyst Pd/MnO prepared in example 1 2 The catalytic efficiency of @ C-600 is highest.
(3) Relation between different Cr (VI) initial concentrations and treatment effects
The catalyst Pd/MnO prepared in example 1 2 The @ C-600 is used for treating Cr (VI) in a water body, and the method is as follows: adding a catalyst and formic acid into a water body containing Cr (VI) pollutants, regulating the pH value of the water body to 2, and carrying out reduction reaction for 2 hours at normal temperature and normal pressure; wherein the concentration of the catalyst was 0.25g/L, and the initial concentration of Cr (VI) was 0.5mM, 1mM, 1.5mM and 2mM, respectively. The test results are shown in FIG. 7.
As can be seen from FIG. 7 (a), under the same reaction conditions, the higher the initial concentration of Cr (VI), the longer the time required for the reduction of Cr (VI) is, the initial activity of the catalyst is gradually increased, and when the initial concentration of Cr (VI) is 0.5mM, the Cr (VI) in the water body can be reduced almost completely within 120 min.
In addition, 1/R in FIG. 7 (b) 0 And 1/C 0 The correlation coefficient of (C) proves that the catalytic hydrogenation reduction reaction of Cr (VI) on the surface of the catalyst accords with a Langmuir-Hinshellwood model.
(4) PH stability test
The catalyst Pd/MnO prepared in example 1 2 The @ C-600 was used to treat Cr (VI) in a body of water with a reaction time of 2 hours, a catalyst concentration of 0.25g/L, an initial concentration of Cr (VI) of 1mM, and a pH of 2, 4, 6 or 10. The test results are shown in FIG. 8.
As can be seen from FIGS. 8 (a) and 8 (b), the treatment effect on Cr (VI) in a water body is best when the pH in the water body is 2.
(5) Cycle stability test
The catalysts prepared in example 1 and comparative example 1 were used to treat Cr (VI) in a water body according to the method described above, wherein the pH was 2, the reaction time was 2 hours, the initial concentration of Cr (VI) was 1mM, and the concentration of the catalyst was 0.25g/L. The test results are shown in fig. 9 and 10.
As can be seen from FIGS. 9 (a) and 9 (b), the catalyst Pd/MnO prepared in example 1 2 Five cyclic reactions are carried out on the @ C-600, and the activity of the catalyst is reduced within 30 percent. As can be seen from FIGS. 10 (a) and 10 (b), the catalyst Pd/MnO prepared in comparative example 1 2 The catalyst activity was reduced by about 50% in the second cycle and 75% in the fifth cycle, indicating that the catalyst Pd/MnO was 2 Is poor in cyclic stability.
The catalysts prepared in examples 2 and 3 were tested for catalytic performance comparable to example 1.
To sum up, pd/MnO 2 Although the catalytic effect is good, the cyclic stability is poor. The surface of the catalyst is modified by coating carbon, so that the binding force between Pd particles and manganese dioxide is improved, the catalyst can be soaked and stirred vigorously under an acidic condition, and good stability is shown; meanwhile, the dispersity and the active sites of the noble metal particles can be improved by introducing the carbon-based functional groups, so that the catalytic performance of the catalyst is improved. Therefore, the catalyst prepared by the method provided by the invention has the advantages of high catalytic efficiency, good cycle stability and catalytic activity, excellent comprehensive performance and good application prospect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (11)
1. A method of treating hexavalent chromium in a water body, the method comprising: treating a water body containing hexavalent chromium pollutants by using a coated Pd-based catalyst;
the preparation method of the coated Pd-based catalyst comprises the following steps:
(1) Will contain starch and PdCl 2 The pH of the mixed solution of (2) is adjusted to 6.5-7.5, and then it is mixed with MnO 2 Mixing materials to obtain a first solution;
(2) Mixing and reacting the first solution with ascorbic acid solution, and then carrying out solid-liquid separation to obtain Pd/MnO 2 A composite material;
(3) The Pd/MnO is added to the catalyst 2 Dispersing the composite material and glucose into water, then carrying out polymerization reaction, and carrying out solid-liquid separation on the obtained reaction liquid to obtain a solid product;
(4) And in the atmosphere of protective gas, heating the solid product to 550-650 ℃ for calcining to obtain the coated Pd-based catalyst.
2. The method of claim 1, wherein in step (1), pdCl is present in the first solution 2 With MnO 2 The mass ratio of the materials is 0.1-0.5: 10.
3. the method of claim 1, wherein in step (2), the MnO in the first solution 2 The mass ratio of the material to the ascorbic acid in the ascorbic acid solution is 10:0.5 to 1.
4. A method according to claim 1 or 3, wherein in step (2) the ascorbic acid solution comprises ascorbic acid, starch and water.
5. A method according to claim 1 or 3, wherein in step (2) the concentration of ascorbic acid in the ascorbic acid solution is from 5 to 20mg/mL.
6. The method according to claim 1, wherein in step (3), the Pd/MnO is as follows 2 Composite material and glucoseAnd water in an amount ratio of 0.5g: 0.8-2 g: 20-40 mL.
7. The method according to claim 1, wherein in the step (3), the polymerization temperature is 150 to 250 ℃ and the polymerization time is 10 to 15 hours during the polymerization reaction.
8. The method of claim 1, wherein step (3) comprises: the obtained reaction liquid was filtered, and the obtained solid phase was washed with water until the filtrate was colorless, and then dried to obtain a solid product.
9. The method of claim 1, wherein in step (4), the shielding gas is N 2 。
10. The method according to claim 1, wherein in the step (4), the calcination time is 3 to 6 hours.
11. The method of claim 1, wherein in step (4), the rate of temperature rise is 4 to 7 ℃/min.
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