CN109046338B - Carbon material immobilized palladium catalyst, preparation and application thereof - Google Patents
Carbon material immobilized palladium catalyst, preparation and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 319
- 239000003054 catalyst Substances 0.000 title claims abstract description 164
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 39
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
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- 235000011613 Pinus brutia Nutrition 0.000 claims description 5
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- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 24
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/613—
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention belongs to the field of wastewater treatment, and particularly relates to a carbon material-supported palladium catalyst, and a preparation method and application thereof. Mixing the biomass material with a palladium salt solution, adjusting the pH value to be alkaline, and carrying out hydrothermal reaction after mixing to obtain a hydrothermal reaction product; then carrying out solid-liquid separation on the hydrothermal reaction product to obtain a solid phase, drying the solid phase and then carrying out heat treatment to obtain the carbon-supported palladium catalyst; correspondingly, the carbon material-immobilized palladium catalyst with large specific surface area, high contact efficiency and high reaction activity is obtained, so that the technical problems of high cost, few reaction sites, low contact efficiency of oxidants, low reaction efficiency, difficult reuse of the catalyst and the like of the existing palladium catalyst used in the advanced oxidation technology are solved.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a carbon material-supported palladium catalyst, and a preparation method and application thereof.
Background
With the development of industries, pesticides, fertilizers and various petroleum-derived material industries, the pollution of organic pollutants such as phenols and the like which are difficult to degrade to water bodies is increasingly serious. Compared with the common sewage, the content of pollutants in the sewage is relatively low, but the sewage is difficult to treat by most sewage treatment systems, and the problem of reaching the standard in advanced treatment is not effectively solved all the time. The probability of digestive cancer is greatly increased for people who drink water containing trace organic pollutants for a long time. At present, several common sewage treatment processes at home and abroad have unsatisfactory treatment effect on pollutants difficult to degrade, for example, a biological method cannot completely remove the pollutants, a membrane method does not fundamentally decompose and remove the pollutants, and the treatment processes such as the biological method, the membrane method and the like have difficulty in meeting the treatment requirements of the pollutants.
In recent years, Advanced Oxidation Processes (AOPs) have been increasingly used in the field of organic wastewater treatment, and the principle thereof is that strongly oxidizing hydroxyl radicals or sulfate radicals and the like generated in the Advanced Oxidation process can indiscriminately oxidize and decompose nondegradable pollutants containing substituents such as carboxyl, sulfo, nitro and the like, and no concentrated solution is generated. However, one of the main problems of the conventional advanced oxidation technology is that the contact efficiency of the oxidation process is too low, the reaction efficiency is limited, and meanwhile, due to the use of a homogeneous reaction system, the catalyst cannot be reused, so that the cost of the advanced oxidation technology is high. The palladium catalyst is widely considered to have a good catalytic effect on persulfate, but the carrying of the palladium catalyst is always a problem to be solved. Some researchers have used Pd supported on powdered alumina, but the reacted Pd catalyst cannot be easily recycled because the alumina powder has a small particle size. More importantly, the surface of the alumina is compact, the alumina is used as a carrier, the cost is high, meanwhile, enough reaction active sites cannot be provided for the subsequent catalytic reaction of the active palladium particles, and the effect is limited.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention provides a carbon material-immobilized palladium catalyst, a preparation method and application thereof, which fully combine the characteristics and the application requirements of the palladium catalyst, and redesign the palladium catalyst-supported carrier and the immobilization mode in a targeted manner, so that the carbon material-immobilized palladium catalyst with large specific surface area, high contact efficiency and high reaction activity is correspondingly obtained, and the technical problems of high cost, fewer reaction sites, low oxidant contact efficiency, low reaction efficiency, difficult catalyst reuse and the like of the existing palladium catalyst used in the advanced oxidation technology are solved.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a palladium catalyst supported on carbon, comprising the steps of:
(1) mixing the biomass material with a palladium salt solution, adjusting the pH value to be alkaline, performing ultrasonic treatment, and performing hydrothermal reaction to obtain a hydrothermal reaction product; the hydrothermal reaction is used for carrying out hydrothermal carbonization on the biomass material and bonding organic functional groups on the surface of the biomass material with palladium;
(2) carrying out solid-liquid separation on the hydrothermal reaction product to obtain a solid phase, drying the solid phase and then carrying out heat treatment to obtain the carbon-supported palladium catalyst; the heat treatment serves to remove bound water from the dried product, to increase the specific surface area of the product, and to increase the binding force of the carbon substrate to palladium.
Preferably, the biomass material in the step (1) is pine sawdust, corncobs, coconut shells or straws, and the average particle size of the biomass material is 75-280 μm.
Preferably, the biomass material of step (1) is pine wood chips.
Preferably, the mass ratio of the biomass material in the step (1) to the palladium salt in the palladium salt solution is 10: 1-1: 1, wherein the solid-to-liquid ratio of the hydrothermal reaction is 1: 5-1: 10.
preferably, the pH value is adjusted to 8.0-10.5 in the step (1).
Preferably, the mixing of step (1) comprises an ultrasonic dispersion step.
Preferably, the ultrasonic dispersion is sonicated for 30 minutes or more.
Preferably, the hydrothermal reaction temperature in the step (1) is 150-250 ℃, and the hydrothermal reaction time is 12-24 hours.
Preferably, the heat treatment temperature in the step (2) is 300-400 ℃, and the heat treatment time is 0.5-2 hours.
According to another aspect of the invention, a carbon material-supported palladium catalyst is provided, which comprises metal palladium particles and a carbon rod, wherein the metal palladium particles are dispersedly coated on the surface of the carbon rod, the length of the carbon rod is 75-280 μm, and the palladium content in the catalyst is 1.5-10 wt%.
Preferably, the specific surface area of the palladium catalyst is 50-200 m2/g。
According to another aspect of the present invention, there is provided a use of the palladium catalyst for treating organic wastewater to degrade organic pollutants therein, specifically: and catalyzing a persulfate system or a Fenton system by using the carbon-supported palladium catalyst to generate active free radicals in situ, and performing oxidation-reduction reaction on the active free radicals and organic matters in the organic sewage to remove the organic matters in the sewage.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the invention provides a preparation method of carbon material immobilized palladium catalyst particles, which is obtained by mixing and dispersing biomass materials in a certain particle size range with palladium salt, then carrying out hydrothermal reaction, and then carrying out thermal treatment. The specific surface area of the prepared catalyst can reach 150m2More than g, good degradation effect when applied to degrading sewage;
(2) the invention provides a carbon material immobilized palladium catalyst, which takes a carbon material as a carrier, realizes the close combination of active palladium particles and a carbon substrate, is uniformly distributed on the surface of the carbon material, greatly increases the contact sites of pollutants and the palladium catalyst when being applied to the degradation of phenolic organic pollutants by virtue of the excellent pore structure, large specific surface area and rich organic functional groups on the surface of the carbon material, increases the generation amount of active free radicals, has high reaction activity and good degradation effect, and has less loss of the active palladium particles during application and can be recycled, thereby greatly reducing the catalyst cost;
(3) the preparation method of the carbon material immobilized palladium catalyst provided by the invention is simple and easy to implement, easy to industrialize and low in cost, and well overcomes the defects of low reaction activity, serious loss and incapability of recycling caused by the lack of effective immobilization of the palladium catalyst in the prior art.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the carbon-supported palladium catalyst of the present invention;
FIG. 2 is a transmission electron microscope image of a carbon material-supported palladium catalyst prepared in example 1;
FIG. 3 is a scanning electron microscope photograph of a carbon material-supported palladium catalyst prepared in example 1;
FIG. 4 is a Fourier Transform Infrared (FTIR) spectrum of a palladium on charcoal catalyst of example 1 and a palladium on charcoal catalyst of comparative example 1;
FIG. 5 is a graph showing the reaction effect of the catalyst under different conditions in example 4;
FIG. 6 is a graph showing the effect of the reaction of different types of catalysts in example 5;
FIG. 7 is a graph of the effect of the treatment of varying amounts of palladium in example 6;
FIG. 8 is a graph showing the effect of the repeated experiments on the palladium-on-activated-carbon and hydrothermal palladium-on-carbon catalysts of example 7.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The carrier with low cost, large specific surface area and high reaction activity is selected as the carrier of the active palladium catalyst, so that the reaction efficiency can be improved to a large extent, the leaching of palladium is reduced, the repeated use of palladium is facilitated, and a reference is provided for the further popularization and application of the advanced oxidation technology. To this end, the present invention provides a carbon-material-supported palladium catalyst in which active palladium particles are uniformThe catalyst is distributed on the surface of a carbon material, wherein the size of the carbon material is 75-280 mu m, and the content of palladium in the catalyst particles is 1.5-10 wt%. The specific surface area of the palladium catalyst particles is 50-200 m2/g。
The preparation method of the carbon material-supported palladium catalyst provided by the invention comprises the following steps:
(1) mixing the biomass material with a palladium salt solution, adjusting the pH value to be alkaline, and carrying out hydrothermal reaction after mixing to obtain a hydrothermal reaction product; the hydrothermal reaction is used for carrying out hydrothermal carbonization on the biomass material, and organic functional groups on the surface of the biomass material are combined with palladium;
(2) carrying out solid-liquid separation on the hydrothermal reaction product to obtain a solid phase, drying the solid phase and then carrying out heat treatment to obtain the carbon-supported palladium catalyst; the heat treatment serves to remove bound water from the dried product, to increase the specific surface area of the product, and to increase the binding force of the carbon substrate to palladium.
The biomass material in the step (1) can be any biomass material, and the preferred biomass material comprises pine sawdust, corncobs, coconut shells or straws, and pine sawdust is further preferred. The biomass material is ground and sieved, and 50-mesh undersize and 200-mesh oversize are selected, namely the average particle size of the biomass material is 75-280 mu m. The biomass material in the size range is selected in order to ensure that when the prepared carbon material formed by the biomass material is used as a solid-supported substrate of the palladium catalyst, the particle size of the finally prepared catalyst is large enough to facilitate the recycling of the catalyst.
The mass ratio of the biomass material in the step (1) to the palladium salt in the palladium salt solution is preferably 10: 1-1: 1, the solid-liquid ratio of the hydrothermal reaction is preferably 1: 5-1: 10.
the pH value is preferably adjusted to 8.0-10.5 in the step (1).
The mixing of step (1) comprises an ultrasonic dispersion step, and the ultrasonic dispersion is preferably ultrasonic for more than 30 minutes. The purpose of ultrasonic dispersion is to fully disperse the wood chips and the active palladium particles, and the particles are uniformly distributed in the solution, so that the wood chips and the active palladium particles are tightly combined in the subsequent hydrothermal process.
The hydrothermal reaction temperature in the step (1) is 150-250 ℃, and the hydrothermal reaction time is 12-24 hours. The hydrothermal method aims to utilize the high temperature and the self-pressure generated by the hydrothermal method to convert the original biomass material to the hydrothermal carbon with a rougher surface and higher functional group content, and the high temperature and the self-pressure are favorable for the adhesion of palladium, namely the close combination of the generated oxygen-containing functional groups and chemical bonds between active palladium particles.
The heat treatment temperature in the step (2) is 300-400 ℃, and the heat treatment time is 0.5-2 hours. The significance of the heat treatment is that on one hand, bound water in the hydrothermal catalyst is further removed, meanwhile, the heat treatment can effectively remove furan, polycyclic aromatic hydrocarbon and other structures in the hydrothermal palladium-charcoal catalyst, and has an obvious effect of improving the specific surface area of the catalyst, and on the other hand, the heat treatment can effectively improve the stability of the hydrothermal palladium-charcoal catalyst in an aqueous phase environment, strengthen the connection between active palladium particles and a carbon substrate, and reduce the loss of palladium in the reaction.
The prior art also reports palladium carbon catalysts, but the palladium carbon catalysts adopt activated carbon with larger specific surface area as a palladium carrier, the activated carbon is prepared at a high temperature of more than 800 ℃, and the palladium carbon catalysts have the following defects: 1) the process is more complex, and the active carbon needs to be burned out at high temperature under the protection of nitrogen and then used as a subsequent process; 2) compared with hydrothermal carbon, the activated carbon has fewer oxygen-containing functional groups due to a high-temperature sintering process, and the reduction of the functional groups reduces the reaction effect on one hand and is not beneficial to the fixation of palladium on the other hand.
According to the invention, a hydrothermal method is adopted, so that the process of converting biomass into active carbon at the early stage is omitted, more importantly, more oxygen-containing functional groups are formed under the hydrothermal condition at high temperature and self pressure, more active palladium particles with higher content are successfully and stably loaded under the same quality, although a part of specific surface area is sacrificed (the active carbon is used as a carrier, experiments prove that the specific surface area is larger), the catalyst obtained by the hydrothermal method can catalyze to generate more active free radicals due to more active palladium components and more surface functional groups, and has a better reaction effect.
By means of hydrothermal high-temperature and high-pressure conditions, the carbon material immobilized palladium catalyst particles prepared by the hydrothermal method have the advantages that active palladium particles are uniformly distributed on the surface of carbon, the size of the carbon material is 75-280 mu m, the palladium content can reach 10%, and the specific surface area can reach 156m2More than g.
The carbon material-supported palladium catalyst particles provided by the invention are used for treating organic sewage and degrading organic pollutants in the organic sewage, and experiments prove that excellent effects are obtained. The carbon material-supported palladium catalyst is used for catalyzing a persulfate system or a Fenton system to generate active free radicals in situ, and the active free radicals and organic matters in the organic sewage are subjected to oxidation-reduction reaction to remove the organic matters in the sewage. The persulfate system is a reaction system which adds persulfate as an oxidant in the system to generate persulfate radicals with strong oxidizing property and is further used for oxidizing and degrading pollutants; the fenton system is a reaction system which utilizes the reaction of ferrous ions and hydrogen peroxide to generate hydroxyl radicals and further treat pollutants.
Taking the persulfate system as an example, the specific application method can comprise the following steps:
(1) adding organic sewage to be treated into a container, adding the prepared carbon-supported palladium catalyst and a certain amount of potassium persulfate; adjusting the pH value of the organic sewage to be treated to 1-7; the pH value of the organic sewage to be treated is preferably adjusted to 5-6.
(2) Utilizing devices such as magnetic stirring and the like, enabling persulfate to generate hydroxyl radicals and sulfate radicals under the palladium catalysis condition, and removing organic pollutants in the organic sewage through oxidation of the hydroxyl radicals and the sulfate radicals;
(3) after the reaction is finished, the solid catalyst is filtered and dried so as to be recycled. The reaction time of the organic sewage in the container is 2-6 hours, and the pollutants can be removed due to the high efficiency of persulfate reaction.
According to the organic sewage treatment method, palladium is used for catalyzing persulfate to generate active free radicals in situ, and the active free radicals and organic matters in the organic sewage are subjected to oxidation-reduction reaction, so that the organic matters in the sewage are removed. The organic sewage is waste water containing organic pollutants, including garbage leachate or other industrial organic waste water. The sewage treatment method mainly aims at the organic pollutants difficult to degrade, and has the main principle that: part of organic pollutants can be directly removed by the surface pore channels of the porous palladium catalyst in an adsorption mode; under the condition of palladium catalysis, persulfate generates a large amount of hydroxyl free radicals and sulfate free radicals, and partial organic pollutants are removed through oxidation.
SO4·-The process of removing organic pollutants by oxidation is as follows:
RH (organic pollutants) + SO4·-→HSO4 -+ R (degradation product)
The invention relates to a process flow for removing pollutants such as organic matters in sewage such as domestic waste leachate, industrial organic wastewater and the like by utilizing palladium loaded on the surface of a carrier of an immobilized palladium catalyst to catalyze persulfate or hydrogen peroxide and utilizing interfacial mass transfer between solid and liquid and related interfacial reaction.
The adoption of the powdery palladium catalyst (the particle size is less than 10 microns) can promote persulfate to generate active free radicals, but the catalyst cannot be recycled at the same time, so that the cost is increased. The invention uses hydrothermal carbon as a carrier for immobilized palladium, and meanwhile, the carrier material can provide a large amount of reaction active sites and has larger specific surface area.
According to the organic sewage treatment method, solid palladium is used for catalyzing persulfate or hydrogen peroxide, and palladium can catalyze persulfate to generate persulfate free radicals and hydrogen peroxide to generate hydroxyl free radicals in the presence of a catalyst. It is believed that a larger specific surface area of the catalyst can be beneficial for the forward direction of the reaction, but too small a solid palladium catalyst is easily lost during the reaction, and does not meet the requirement for repeated use of such more expensive metal catalysts. Therefore, the volume of the solid catalyst should be reduced as much as possible while ensuring that the metal catalyst does not lose a large amount as the reaction proceeds. According to the invention, the palladium catalyst is designed automatically, metal palladium is immobilized on the surface of the hydrothermal carbon, the particle size is 75-280 μm, and the loss of the catalyst can be well controlled while the reaction effect is ensured. On the other hand, the invention utilizes hydrothermal reaction to inhibit the loss of organic functional groups on the surface of the carbon material, and experiments prove that the great amount of the organic functional groups is favorable for the load combination of palladium, and compared with the carbon material with large specific surface area, the catalytic effect of the catalyst obtained by the chemical action of the palladium on the surface of the carbon material through the organic functional groups is far better than that of the catalyst obtained by the carbon material with large specific surface area through physical adsorption and palladium immobilization.
The sewage treatment method solves the technical problems that the traditional Fenton method and Fenton-like water treatment technology thereof are difficult to solve for a long time, the efficiency between the oxidant and the catalyst is low, and the catalyst is difficult to reuse for multiple times. The invention creatively attaches the palladium catalyst required by the reaction to the surface of the carbon material carrier, and further decomposes and generates hydroxyl free radicals and sulfate free radicals with strong oxidizing property as oxidizing components through the synergistic effect of the catalytic oxidant, thereby achieving the purpose of efficiently treating the organic wastewater, simultaneously achieving the condition of effectively and repeatedly using the catalyst, saving the cost of advanced oxidation technology, and having the feasibility of industrial application.
The invention belongs to the field of wastewater treatment, and particularly relates to a carbon material-immobilized palladium catalyst particle material, and a preparation method and application thereof. The immobilized palladium catalyst provided by the invention takes a carbon material as a carrier, utilizes rich organic functional groups on the surface of charcoal, realizes stable immobilization of active palladium particles on the surface of the charcoal material on the charcoal surface, greatly increases contact sites of pollutants and the palladium catalyst when being applied to degradation of organic pollutants which are difficult to degrade, such as phenols and the like, by virtue of the excellent pore structure and the larger specific surface area of the charcoal material, increases the generation amount of active free radicals, has high reaction activity and good degradation effect, and has less loss of the palladium catalyst when being applied because the palladium catalyst particles are stably immobilized on the surface of the charcoal material, and can be recycled. The invention provides a palladium catalyst, which comprises active component metal palladium ions and a carbon carrier, wherein the mass fraction of active metal palladium particles in the prepared catalyst is 1.5-10%. The invention also provides a preparation method of the palladium catalyst, which comprises the following steps: mixing and stirring palladium salt and a biomass raw material under an alkaline condition, carrying out ultrasonic treatment on the obtained mixture, carrying out hydrothermal reaction, and sequentially carrying out suction filtration, cleaning and heat treatment on the obtained material to obtain the palladium catalyst. The invention utilizes rich oxygen-containing functional groups on the surface of the hydrothermal carbon and high temperature and self-pressure generated in the hydrothermal process to realize the tight combination of the nano-scale palladium particles and the carbon carrier, so that the nano-scale palladium particles are uniformly distributed on the surface of the carrier. The catalyst is adopted to treat the wastewater, and has higher reaction activity and better degradation effect. At the same time. Through the close combination of carbon and palladium, the usage amount of corresponding palladium salt is reduced, the loss of active ingredients is reduced, and the reuse ratio of the catalyst is improved.
The following are examples:
example 1
A preparation method of a carbon material-supported palladium catalyst is shown in figure 1, and comprises the following steps:
(1) mixing wood chips and palladium salt, adjusting the pH value to 10.0, stirring for 3 hours at normal temperature by using a magnetic stirrer, and then putting the mixed mixture into ultrasound for 40min to uniformly disperse Pd and wood chips. Putting the mixture subjected to ultrasonic treatment into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, carrying out vacuum filtration, and drying to obtain a hydrothermal reaction product; screening the wood chips, selecting 50-mesh undersize materials and 200-mesh oversize materials, namely selecting the wood chips with the particle size range of 75-280 mu m, wherein the mass ratio of the palladium salt to the wood chips is 1: 10, wherein the solid-liquid ratio of the hydrothermal reaction is 1: 10, the prepared catalyst has better performance,
(2) and carrying out solid-liquid separation on the hydrothermal reaction product to obtain a solid phase, drying, and heating at 300 ℃ for 1 hour to obtain the palladium catalyst particles.
The carbon material supported palladium catalyst particles prepared by the hydrothermal method comprise Pd active particlesThe TEM image is shown in fig. 2, and it can be seen from fig. 2 that the black particles are activated palladium particles, while the dark gray material of the background is the carbon substrate, and the activated palladium particles are uniformly dispersed on the surface of the carbon material. FIG. 2 is a SEM image of the palladium catalyst, in which the carbon material base is in the shape of a nearly rod, the length of the carbon rod is 75 to 280 μm, the palladium content is 8.22%, and the specific surface area is 156m2More than g.
Comparative example 1
A preparation method of an activated carbon-supported palladium catalyst comprises the following steps:
other conditions for preparing the pyrolytic carbon are the same as those for preparing the hydrothermal carbon supported palladium catalyst in example 1, the only change is that the carrier needs to be prepared in advance under the protection of nitrogen, and the specific preparation steps are as follows:
(1) putting the wood chips into a nitrogen furnace, adjusting the flow rate of nitrogen to be 5m L/min, heating to 400 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 1h to prepare an activated carbon material, wherein the particle size of the prepared activated carbon is about 100 mu m;
(2) mixing the prepared activated carbon and palladium salt, adjusting the pH value to 10.0, stirring for 3 hours at normal temperature by a magnetic stirrer, and then putting the mixed mixture into ultrasound for 40min to uniformly disperse Pd and the activated carbon. And (3) performing vacuum filtration and drying on the mixture subjected to ultrasonic treatment to obtain a reaction product, wherein the mass ratio of the palladium salt to the active carbon is 1: 10, placing the mixture subjected to ultrasonic treatment into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, carrying out vacuum filtration, and drying to obtain a hydrothermal reaction product, wherein the solid-to-liquid ratio of the hydrothermal reaction is 1: 10.
(3) and carrying out solid-liquid separation on the hydrothermal reaction product to obtain a solid phase, drying, and heating at 300 ℃ for 1 hour to obtain the palladium catalyst particles.
The activated carbon palladium catalyst prepared in comparative example 1 and the hydrothermal carbon palladium catalyst prepared in example 1 were subjected to tests of respective parameters and compared, and specific results are shown in table 1.
TABLE 1 palladium on activated carbon catalyst prepared in comparative example 1
Comparison of various parameters with the hydrothermal palladium on charcoal catalyst prepared in example 1
FIG. 4 is a Fourier Transform Infrared (FTIR) spectrum of palladium-on-activated-carbon and hydrothermal palladium-on-carbon catalysts. From fig. 4, it can be seen that both the palladium on activated carbon and the palladium on hydrothermal carbon catalysts contain various oxygen-containing functional groups. However, the amount of functional groups of the catalysts prepared in example 1 and comparative example 1 can be quantitatively analyzed by Boehm titration, and the results are shown in table 2:
TABLE 2 palladium on activated carbon catalyst prepared in comparative example 1 with
Comparison of the amount of functional groups of the hydrothermal Palladium on carbon catalyst prepared in example 1
As can be seen from tables 1 and 2, the carbon material-supported palladium catalyst prepared by the hydrothermal method of the present invention has a lower specific surface area, pore volume and width than the comparative activated carbon-supported palladium catalyst, but the hydrothermal carbon-supported palladium catalyst prepared by the present invention has a higher palladium loading amount and more organic functional groups.
Example 2
A preparation method of carbon material-supported palladium catalyst particles comprises the following steps:
(1) the method comprises the steps of grinding dried corncobs, mixing 50-mesh undersize and 200-mesh oversize (with particle size of 75-280 mu m) with palladium salt, adjusting pH to 10.0, stirring for 2 hours at normal temperature by using a magnetic stirrer, and then ultrasonically treating the mixed mixture for 30 minutes to uniformly disperse Pd and the biomass material. Putting the mixture subjected to ultrasonic treatment into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 200 ℃, carrying out vacuum filtration, and drying to obtain a hydrothermal reaction product; the mass ratio of the palladium salt to the wood dust is 1: 10, wherein the solid-liquid ratio of the hydrothermal reaction is 1: 5, the prepared catalyst has better performance,
(2) and carrying out solid-liquid separation on the hydrothermal reaction product to obtain a solid phase, drying, and heating at 400 ℃ for 0.5 hour to obtain the palladium catalyst particles.
Experiments prove that the material prepared under the condition also has better catalytic activity.
Example 3
The carbon-supported palladium catalyst particles obtained in example 1 were used for treating organic wastewater, which was obtained from refuse leachate from municipal solid waste landfills, had a COD of 391 to 445 mg/L and a pH of 7.6 to 8.2, and 2000m L of the leachate was placed in a beaker.
The palladium content of the hydrothermal carbon-carried palladium catalyst is 8.22%, the dosage of PMS is controlled to be 2.0 g/L, 0.5 g/L of catalyst is added, the reaction temperature is set to be 25 ℃, samples are respectively taken in 30min, 60min, 90min and 120min, and the processing results are shown in the following table:
TABLE 3 Effect of different times on COD removal
| Time (min) | 30 | 60 | 90 | 120 |
| Contaminant removal Rate (%) | 67.6 | 82.2 | 100.0 | 100.0 |
Comparative example 2
The same organic wastewater as in example 7 was treated with the purchased alumina-supported palladium catalyst, in which the palladium content was 10.0% and the catalyst amount was 0.5 g/L and 2.0 g/L. the reaction temperature was set at 25 ℃ and samples were taken at 30min, 60min, 90min and 120min, respectively, and the treatment results are shown in the following table:
TABLE 1 Effect of different times on COD removal
| Time (min) | 30 | 60 | 90 | 120 |
| Contaminant removal Rate (%) | 54.8 | 79.6 | 92.3 | 100.0 |
It can be seen that the commercial palladium-on-alumina catalyst has similar performance to the hydrothermal palladium-on-carbon catalyst obtained in example 1 under the same experimental conditions, and the catalyst itself has higher palladium loading, so the effect is also ideal. The hydrothermal carbon palladium catalyst prepared in example 1 achieves a faster reaction effect due to a higher specific surface area and abundant functional groups, although the loading amount of palladium does not reach 10%, and the degradation of pollutants is completed within 90 min.
Example 4
In order to verify the adsorption effect of the hydrothermal palladium carbon catalyst per se and the adsorption effect of the functional group, and the reaction effect under the condition without an oxidant (here, PMS is used), at room temperature (25 ℃), the landfill leachate described in example 3 is used, the hydrothermal palladium carbon-loaded palladium catalyst obtained in example 1 (palladium content is 8.22%), the amount of the reactive PMS is 2.0 g/L, and the amount of the added catalyst is 0.5 g/L, and the removal effects of the pollutants under the conditions of only PMS, only hydrothermal palladium carbon catalyst, PMS and hydrothermal palladium carbon catalyst are respectively tested, the samples are respectively sampled at 5min, 10min, 20min, 40min, 60min, 80min and 100min, and the ordinate is the ratio of the measured pollutant concentration to the original pollutant concentration, and the obtained results are shown in fig. 5.
Through data analysis, under the condition of only PMS, the reaction effect is slow, and basically no obvious degradation effect exists; only under the condition of a hydrothermal carbon palladium catalyst, the reaction effect is very common, and the maximum removal effect is about 35 percent, which shows that the adsorption capacity is common; when both PMS and hydrothermal palladium on charcoal exist, the removal rate basically reaches 100%, which shows the good catalytic effect of the hydrothermal palladium on charcoal catalyst.
Example 5
In order to verify the contents of Pd in the hydrothermal carbon, the activated carbon palladium catalyst, the hydrothermal carbon palladium catalyst and the palladium chloride (the purity is more than 99.0%), wherein the contents of Pd in the hydrothermal carbon palladium catalyst, the activated carbon palladium catalyst and the palladium chloride are converted into the adding concentrations of 8.22% according to the corresponding concentrations, and the removal effects of the five catalysts on pollutants are compared, the landfill leachate described in example 3 is used, the dosage of the reaction PMS is 2.0 g/L, the dosage of the adding catalyst is 0.5 g/L, the activated carbon palladium catalyst obtained in comparative example 1 and the intermediate product of the two are used, the removal effects of the pollutants are compared together by the activated carbon and the hydrothermal carbon without palladium addition, the samples are respectively sampled and tested at the time of 5min, 10min, 20min, 40min, 60min, 80min and 100min, and the ordinate is the ratio of the measured pollutant concentration to the original pollutant concentration, and the obtained result is shown in FIG. 6.
Through data analysis, under the condition of only activated carbon, although the specific surface area is higher, the removal effect is limited, and the specific surface area is not as high as that of the hydrothermal carbon, which indicates that the specific surface area is not as high as that of the functional group which is more in number and is more helpful for the degradation of pollutants; the best removal effect is obtained by adopting the palladium chloride powder, but the particle size of the palladium chloride powder is small and the palladium chloride powder cannot be recycled; the hydrothermal carbon catalyst has good effect similar to palladium chloride powder, but has larger particle size, is convenient to recover and has feasibility of industrial utilization.
Example 6
In order to verify the effect of different loading amounts of the hydrothermal palladium-carbon catalyst on pollutant removal, hydrothermal carbon (palladium loading amount is 0%), hydrothermal palladium-carbon (1.5%), namely palladium loading amount is 1.5%, hydrothermal palladium-carbon (2.5%), namely palladium loading amount is 2.5%, hydrothermal palladium-carbon (5%), namely palladium loading amount is 5%, hydrothermal palladium-carbon (10%), namely palladium loading amount is 10%, and the pollutant removal effect of five catalysts is compared, the landfill leachate described in example 3 is used, the reaction PMS dosage is 2.0 g/L, the added catalyst dosage is 0.5 g/L, and the results are shown in fig. 7, wherein the samples are taken at 5min, 10min, 20min, 40min, 60min, 80min and 100min and the ordinate is the ratio of the measured pollutant concentration to the original pollutant concentration.
Through data analysis, it can be found that when the loading amount of palladium of the catalyst is less than 10%, the removal effect is obviously improved along with the increase of the loading amount, when the loading amount is 10%, the effect is the best, and the removal rate reaches 100%, but the difference between the two catalysts with the loading amounts of 10% and 5% does not have a similar trend under the condition of the embodiment, which indicates that the increase ratio of the loading amount is not necessarily favorable for the reaction, and the reason may be that along with the increase of the loading amount, the pore channels with inherently higher specific surface area are blocked, and simultaneously the functional groups are all occupied by active palladium particles, thereby affecting the effect of the catalyst to a certain extent. Since the 10% loading of catalyst costs twice as much as the 5% loading of catalyst, a 5% loading of catalyst is preferred as the catalyst for the reaction under the conditions of this example.
Example 7
In order to verify the repeatable performance of the hydrothermal palladium-on-carbon catalyst and the active palladium-on-carbon catalyst, the landfill leachate described in example 7 is used, the dosage of the reaction PMS is 2.0 g/L, the dosage of the added catalyst is 0.5 g/L, the catalyst is subjected to a repeatability experiment, the catalyst after each experiment is taken out, washed with distilled water for three times, and put into a drying oven for drying for 24 hours, and then a next cycle experiment is carried out, wherein the ordinate is the efficiency of the catalyst, the first cycle default is that the efficiency is 100%, the subsequent catalytic effect and the ratio thereof can obtain the recycling performance of the catalyst, and the loss condition of active ingredients in the catalyst can be reflected from another angle, and the obtained result is shown in FIG. 8.
Through data analysis, the hydrothermal palladium carbon catalyst has better repeatable performance, and the hydrothermal palladium carbon catalyst still has 90% of catalytic performance after reaction is repeated for 6 times, at the moment, the degradation efficiency of the active palladium carbon catalyst is only less than 50%, which shows that active palladium particles can be effectively and stably loaded on the carbon surface through the hydrothermal carbon process, and the active palladium particles have higher activity along with the reaction, less loss and better repeatability.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a carbon material-supported palladium catalyst is characterized by comprising the following steps:
(1) mixing the biomass material with a palladium salt solution, adjusting the pH value to be alkaline, and carrying out hydrothermal reaction after mixing to obtain a hydrothermal reaction product; the hydrothermal reaction is used for carrying out hydrothermal carbonization on the biomass material and bonding organic functional groups on the surface of the biomass material with palladium; the mass ratio of the biomass material to the palladium in the palladium salt solution is 10: 1-1: 1; the hydrothermal reaction temperature is 150-250 ℃;
(2) carrying out solid-liquid separation on the hydrothermal reaction product to obtain a solid phase, drying the solid phase and then carrying out heat treatment to obtain the carbon-supported palladium catalyst; the heat treatment temperature is 300-400 ℃; the heat treatment serves to remove bound water from the dried product, to increase the specific surface area of the product, and to increase the binding force of the carbon substrate to palladium.
2. The preparation method according to claim 1, wherein the biomass material in the step (1) is pine sawdust, corncobs, coconut shells or straws, and the average particle size of the biomass material is 75-280 μm.
3. The preparation method according to claim 1, wherein the hydrothermal reaction in the step (1) has a solid-to-liquid ratio of 1: 5-1: 10.
4. the method according to claim 1, wherein the pH in the step (1) is adjusted to 8.0 to 10.5.
5. The method of claim 1, wherein the mixing of step (1) comprises an ultrasonic dispersion step.
6. The preparation method according to claim 1, wherein the hydrothermal reaction time in the step (1) is 12 to 24 hours.
7. The method according to claim 1, wherein the heat treatment time in the step (2) is 0.5 to 2 hours.
8. The carbon-material-supported palladium catalyst prepared by the preparation method according to any one of claims 1 to 7, comprising metal palladium particles and a carbon rod, wherein the metal palladium particles are dispersedly coated on the surface of the carbon rod, the length of the carbon rod is 75 to 280 μm, and the palladium content in the catalyst is 1.5 to 10 wt%.
9. The palladium catalyst of claim 8, wherein the specific surface area of the palladium catalystIs 50 to 200m2/g。
10. Use of a palladium catalyst according to claim 8 or 9, for treating organic effluents to degrade the organic pollutants therein, in particular: and catalyzing a persulfate system or a Fenton system by using the carbon-supported palladium catalyst to generate active free radicals in situ, and performing oxidation-reduction reaction on the active free radicals and organic matters in the organic sewage to remove the organic matters in the sewage.
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