CN114643067A - Activated and regenerated noble metal catalyst and preparation method and application thereof - Google Patents
Activated and regenerated noble metal catalyst and preparation method and application thereof Download PDFInfo
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- 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
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- B01D2257/00—Components to be removed
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Abstract
The invention discloses an activated and regenerated noble metal catalyst and a preparation method and application thereof. The activation method of the noble metal catalyst comprises the following steps: reacting a noble metal catalyst with an activating agent in a solvent; wherein the activating agent is one or more of borohydride, hydrazine hydrate, formaldehyde, formic acid and glycol; the molar volume ratio of the activating agent to the solvent is 1mol/L or more. The activated noble metal catalyst and/or the regenerated noble metal catalyst obtained by the activation method have relatively ideal catalytic performance, and the catalytic performance can be kept stable; the activation method has the advantages of wide application range, simple operation, low cost and easy realization of amplification application.
Description
Technical Field
The invention particularly relates to an activated and regenerated noble metal catalyst, and a preparation method and application thereof.
Background
With the increasing industrial level, the environmental pollution problem caused by the excessive discharge of Volatile Organic Compounds (VOCs) has attracted much attention. The noble metal catalyst is widely applied to catalytic oxidation of VOC in the environment in the market due to extremely high catalytic activity. However, the actual catalytic conditions are complex, the temperature is not completely controllable, the reaction gas is complex, and phenomena of precious metal sintering, carbon deposition or precious metal poisoning and the like often occur, so that the surface active sites of the catalyst are reduced, the catalytic activity is reduced, and even the activity is lost. The content of noble metals on the earth is scarce and the price is high, and the improvement of the utilization rate of the noble metal catalyst has important significance for sustainable development.
The service life of the commercial noble metal catalyst is about 1-4 years, the inactivated treatment means usually comprises the recovery of noble metals or the regeneration treatment of the noble metals, and the conventional noble metal recovery technology mainly comprises the hydrometallurgy and pyrometallurgy recovery, but the recovery efficiency is low and the recovery cost is high; however, there are great gaps in the research on the improvement of the utilization rate of the noble metal in the noble metal catalyst and the regeneration of the deactivated noble metal catalyst. At present, the regeneration treatment means commonly used in industrial application mainly comprises high-temperature calcination in a dry air atmosphere, high-temperature calcination in a wet air atmosphere and the like, however, the regeneration means has many disadvantages, the method is mainly suitable for the inactivation of the noble metal catalyst caused by carbon deposition, the high-temperature calcination aggravates noble metal sintering, and the damage to the carrier is very serious. Moreover, the deactivation of the noble metal catalyst is not solely due to carbon deposition, but is often the result of a combination of factors, such as sintering deactivation or poisoning deactivation. The activation of deactivated noble metal catalysts caused by sintering or poisoning is rarely reported.
Therefore, there is a need in the art to develop an activation method that is easy to operate, low in cost, and effective in activating a noble metal catalyst that has been deactivated for various reasons.
Disclosure of Invention
The invention aims to solve the technical problems that the activation method of the inactivated noble metal catalyst in the prior art is mainly suitable for the inactivated noble metal catalyst caused by carbon deposition, has poor activation effect on the inactivated noble metal catalyst caused by sintering or toxicity, has the defects of high temperature in the activation process, damage to the noble metal catalyst and a carrier structure and the like, and provides the activated and regenerated noble metal catalyst, and the preparation method and the application thereof. The activated noble metal catalyst and/or the regenerated noble metal catalyst obtained by the activation method have relatively ideal catalytic performance, and the catalytic performance can be kept stable; the activation method has the advantages of wide application range, simple operation, low cost and easy realization of amplification application.
The invention solves the technical problems through the following technical scheme.
The invention provides an activation method of a noble metal catalyst, which comprises the following steps: reacting a noble metal catalyst with an activating agent in a solvent; wherein the activating agent is one or more of borohydride, hydrazine hydrate, formaldehyde, formic acid and glycol; the molar volume ratio of the activating agent to the solvent is 1mol/L or more.
In the present invention, the activating agent is preferably borohydride, more preferably sodium borohydride and/or potassium borohydride.
In the present invention, the solvent may be a solvent which is conventionally used in the art and can completely dissolve the activator without chemically reacting with the catalyst and the activator, and is preferably one or more of water, methanol, ethanol, and tetrahydrofuran, and more preferably water.
In the present invention, the molar volume ratio of the activating agent to the solvent is preferably 2mol/L or more, more preferably 2 to 5mol/L, for example 3 mol/L. When the molar volume ratio of the activating agent to the solvent is less than 0.01mol/L, the activating effect is not preferable.
In the present invention, the mass ratio of the noble metal to the activator in the noble metal catalyst may be conventional in the art, and is preferably 1: (1000 to 1500), more preferably 1: (1200-1500).
In the present invention, the noble metal catalyst may be a fresh noble metal catalyst and/or a deactivated noble metal catalyst. Wherein, according to the routine in the field, the fresh noble metal catalyst generally refers to a catalyst which does not participate in the over-catalytic reaction and has catalytic activity; the deactivated noble metal catalyst generally refers to a catalyst that has been deactivated by participating in a over-catalyzed reaction.
The deactivation cause of the deactivated noble metal catalyst can be a conventional cause of the catalyst field causing the activity reduction of the noble metal catalyst in the catalytic reaction process, and is generally one or more of sintering deactivation, poisoning deactivation and carbon deposition deactivation.
In the present invention, the noble metal in the noble metal catalyst may be a noble metal conventionally used in the catalyst field, preferably one or more of Pt, Pd, Ru, Rh, Au, Ag and Ir, more preferably one or more of Pt, Pd and Ru, for example, "a mixture of Pt and Pd" or "a mixture of Pt and Ru".
Wherein, when the noble metal in the noble metal catalyst is a mixture of Pt and Ru, the mass ratio of Pt and Ru may be conventional in the art, and is preferably 1: (0.25 to 4), preferably 1: 2.
wherein, when the noble metal in the noble metal catalyst is a mixture of Pt and Pd, the mass ratio of Pt and Pd may be conventional in the art, and is preferably 1: (0.25 to 4), more preferably 1: 1.
in the present invention, "activation" in the activation method of the noble metal catalyst may be a process of increasing catalytically active sites in the deactivated noble metal catalyst and/or the fresh noble metal catalyst, which is conventionally recognized by those skilled in the art.
In the present invention, the noble metal catalyst may further include a catalyst carrier and/or a catalyst promoter.
Wherein the catalyst support may be a support conventionally used in the field of noble metal catalysts, for example, Mg2Al4Si5O18。
The wall thickness of the catalyst carrier can be conventional in the art, and is preferably 0.1 to 0.2mm, and more preferably 0.15 to 0.18 mm.
Wherein, the shape of the catalyst carrier may be conventional in the art, preferably one or more of powder, granule, rod and honeycomb, more preferably honeycomb.
The catalyst promoter may be a promoter conventionally used in the field of noble metal catalysts for improving the catalytic activity or selectivity of the noble metal catalyst, for example, cerium oxide and/or zirconium oxide.
In the invention, when the noble metal catalyst is a fresh noble metal catalyst, the material prepared after the reaction is an activated noble metal catalyst.
In the invention, when the noble metal catalyst is an inactivated noble metal catalyst, the material prepared after the reaction is a regenerated noble metal catalyst.
In the present invention, the reaction conditions and methods may be those conventional in the art for such reactions, and are generally carried out under ultrasonic conditions. When the reaction is carried out under the ultrasonic condition, the surface of the inactivated noble metal catalyst is favorable for blocking the pore canal of the catalyst, and deposited carbon covering the active site falls off; sonication also helps the activator to fully react with the noble metal catalyst.
In the present invention, the reaction temperature may be a temperature conventional in the art, preferably 15 to 100 ℃, and more preferably 25 to 50 ℃.
In the present invention, the reaction time can be the time conventionally used in the art, and is preferably 0.5 to 48 hours, and more preferably 1 to 4 hours.
In the present invention, the operation of the reaction may further include washing and/or drying.
Wherein the purpose of the water washing is to remove the activator remaining on the surface of the reacted material. The number of water washes may be conventional in the art, generally leaving the surface of the noble metal catalyst free of the activator residue, and is generally greater than or equal to three.
The drying conditions and methods may be those conventional in such operations in the art, and are typically carried out in an oven.
Wherein, the heating rate of the drying can be conventional in the art, preferably 1 to 10 ℃/min, more preferably 1 to 2 ℃/min.
The drying temperature may be a temperature conventionally used in the art, and is preferably 60 to 200 ℃, and more preferably 60 to 120 ℃.
The drying time can be the time of the operation routine in the field, preferably 4-12 h, more preferably 8-12 h.
The present invention also provides an activated noble metal catalyst and/or a regenerated noble metal catalyst, which is produced by the method for activating a noble metal catalyst as described above.
The invention also provides an application of the activated noble metal catalyst and/or the regenerated noble metal catalyst as a catalyst for catalyzing the oxidation reaction of organic compounds.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the activation process of the present invention can effectively activate fresh noble metal catalysts and/or deactivate noble metal catalysts. Aiming at the inactivated noble metal catalyst caused by various reasons, the activation method can recover the catalytic activity of the inactivated noble metal catalyst to more than 99 percent of that of the fresh noble metal catalyst; the catalytic performance of the fresh noble metal catalyst after activation is obviously improved; the method has the advantages of wide application range, safety, low treatment cost and easy realization of amplification application.
Drawings
FIG. 1 is a graph showing the oxidation of toluene to CO at different temperatures using the regenerated Pt-Ru noble metal catalyst prepared in example 1 and comparative example 3, the deactivated Pt-Ru noble metal catalyst prepared in comparative example 1, and the fresh Pt-Ru noble metal catalyst prepared in comparative example 22Conversion curve of the reaction;
FIG. 2 is a stability curve of the catalytic performance of the regenerated Pt-Ru noble metal catalyst prepared in example 1 at different temperatures;
FIG. 3 shows the oxidation of toluene to CO at different temperatures using the activated Pt-Ru noble metal catalyst of example 2 and the fresh Pt-Ru noble metal catalyst of comparative example 22Conversion curve of the reaction;
FIG. 4 is a graph showing the oxidation of toluene to CO catalyzed by the regenerated Pt-Pd noble metal catalyst obtained in example 3 and comparative example 6, the deactivated Pt-Pd noble metal catalyst obtained in comparative example 4, and the fresh Pt-Pd noble metal catalyst obtained in comparative example 5, respectively, at different temperatures2Conversion curve of the reaction;
FIG. 5 is a stability curve of the catalytic performance of the regenerated Pt-Pd noble metal catalyst prepared in example 3 at different temperatures;
FIG. 6 shows the oxidation of toluene to CO catalyzed by the activated Pt-Pd noble metal catalyst of example 4 and the fresh Pt-Pd noble metal catalyst of comparative example 5 at different temperatures2Conversion curve of the reaction;
FIG. 7 shows that the regenerated Pt-Pd noble metal catalysts prepared in examples 3 and 5-6 and comparative examples 7-8 respectively catalyze the oxidation of toluene to CO at different temperatures2Conversion curve of the reaction;
FIG. 8 is a scanning electron microscope image of the surface morphology of the deactivated Pt-Ru noble metal catalyst and the regenerated Pt-Ru noble metal catalyst of example 1;
FIG. 9 is an XPS plot of Ru 3p for the regenerated Pt-Ru noble metal catalyst from example 1, the deactivated Pt-Ru noble metal catalyst from comparative example 1, and the fresh Pt-Ru noble metal catalyst from comparative example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The deactivated Pt-Ru noble metal catalyst used in the following example 1 is a catalyst deactivated by certain environmental protection technology Co., Ltd in Shanghai in the process of industrial treatment of exhaust gas, and the exhaust gas air volume in the catalytic process is 1900Nm3H is used as the reference value. Due to the fact that gas components in the actual waste gas treatment process are complex (the waste gas components are shown in table 1), especially trichloroethylene and tetrachloroethylene easily cause chlorine poisoning of the noble metal catalyst, so that the activity of the noble metal catalyst is reduced, and even the noble metal catalyst loses activity. In order to research whether the deactivation of the catalyst is related to chlorine poisoning, the deactivated Pt-Ru noble metal catalyst is placed into deionized water for ultrasonic treatment, and the obtained liquid is tested for ICP (inductively coupled plasma) to find that the Cl element content reaches 5.11mg/L, thereby proving that the deactivation is related to chlorine poisoning. Meanwhile, comparing the surface topography of the catalyst before and after deactivation (see figure 8 in detail), a scanning electron micrograph is shown in figure 8, in FIG. 8, a (30 times enlarged view) and c (2000 times enlarged view) correspond to the surface morphology of a fresh Pt-Ru noble metal catalyst, b (30 times enlarged view) and d (2000 times enlarged view) correspond to the surface morphology of an inactivated Pt-Ru noble metal catalyst, compared with the fresh Pt-Ru noble metal catalyst, the inactivated Pt-Ru noble metal catalyst can clearly see that a plurality of cracks appear on the surface when being enlarged by 30 times, and can clearly see that alumina particles become larger when being enlarged by 2000 times, so that an obvious sintering phenomenon exists. The incompletely controllable high temperature of the noble metal catalyst during the use is the main reason for sintering. Meanwhile, XRF test results show that the C content in the noble metal catalyst before and after catalysis is increased from 3.10% to 4.73%, and the deactivation is proved to be related to the carbon deposition of the noble metal catalyst. In summary, the deactivation of the deactivated Pt-Ru noble metal catalyst used in example 1 was caused by sintering, noble metal chlorine poisoning, and carbon deposition.
The reason for the deactivation of the deactivated Pt — Pd noble metal catalyst in example 3 was analyzed by the above method, and the result was also caused by sintering, noble metal chlorine poisoning, and carbon deposition in the same manner as in example 1.
TABLE 1
| Kind of exhaust gas | Maximum concentration (mg/m)3) |
| Methyl isobutyl ketone | 1635.74 |
| Xylene | 1813.68 |
| Ethylbenzene production | 1507.78 |
| Methacrylic acid methyl ester | 367.36 |
| Methanol | 230.03 |
| Toluene | 168.69 |
| Tetrachloroethylene | 71.64 |
| Trichloroethylene | 71.56 |
| Isopropanol (I-propanol) | 54.52 |
| Phenol as the starting material | 40.89 |
| Methacrylic acid (MAA) | 38.17 |
| Butanone | 16.36 |
| Nitrile butadiene | 12.95 |
| Cyclohexanone | 1.23 |
| Total up to | 6030.60 |
Example 1
The above-purchased deactivated Pt-Ru noble metal catalyst for treating VOCs industrially has a catalyst carrier of 200-mesh cordierite (Mg)2Al4Si5O18) The catalyst promoter comprises cerium oxide (CeO)2) And zirconium oxide (ZrO)2) The noble metal comprises 100g/m3Wherein the mass ratio of Pt to Ru is 1: 2, the wall thickness of the honeycomb carrier is 0.15 mm; blowing off dust in pores of the deactivated Pt-Ru noble metal catalyst by using a blower to prepare for later use;
preparing 2.0mol/L sodium borohydride aqueous solution, keeping the temperature to 50 ℃, putting the inactivated Pt-Ru noble metal catalyst into the aqueous solution, wherein the mass ratio of the total mass of Pt and Ru to the mass of sodium borohydride is 1: 1200; carrying out reaction for 1h under the ultrasonic condition; then, repeatedly cleaning the mixture for more than 3 times by using deionized water to ensure that sodium borohydride does not remain on the surface of the prepared material; and drying the obtained product in a 60 ℃ oven for 8 hours at the heating rate of 2 ℃/min to obtain the regenerated Pt-Ru noble metal catalyst.
Example 2
The fresh Pt-Ru noble metal catalyst is adopted and is obtained by the same batch production as the fresh Pt-Ru noble metal catalyst before the inactivation of the inactivated Pt-Ru noble metal catalyst in the embodiment 1;
preparing 2.0mol/L sodium borohydride aqueous solution, keeping the temperature to 50 ℃, putting the fresh Pt-Ru noble metal catalyst into the aqueous solution, wherein the mass ratio of the total mass of Pt and Ru to the mass of sodium borohydride is 1: 1200; carrying out reaction for 1h under the ultrasonic condition; then, repeatedly cleaning the mixture for more than 3 times by using deionized water so as to ensure that sodium borohydride does not remain on the surface of the prepared material; drying the catalyst in a 60 ℃ oven for 8h at the heating rate of 2 ℃/min to obtain the activated Pt-Ru noble metal catalyst.
Example 3
The deactivated Pt-Pd noble metal catalyst which is purchased from the industry and used for treating VOCs is adopted, and the catalyst carrier is 200-mesh cordierite (Mg)2Al4Si5O18) The catalyst promoter comprises cerium oxide (CeO)2) Zirconium oxide (ZrO)2) The noble metal comprises 120g/m3Wherein the mass ratio of Pt to Pd is 1: 1, the wall thickness of the honeycomb carrier is 0.18 mm; blowing off dust in pores of the deactivated Pt-Pd noble metal catalyst by using a blower to prepare for later use;
preparing 2.0mol/L potassium borohydride aqueous solution, keeping the temperature to 25 ℃, putting the inactivated Pt-Pd noble metal catalyst into the aqueous solution, wherein the mass ratio of the total mass of Pt and Pd to the mass of potassium borohydride is 1: 1200; carrying out reaction for 4h under the ultrasonic condition; then repeatedly cleaning for more than 3 times by using deionized water to ensure that no potassium borohydride remains on the surface of the prepared material; drying for 8h at 120 ℃ in a drying oven, wherein the heating rate of the drying oven is 2 ℃/min, and preparing the regenerated Pt-Pd noble metal catalyst.
Example 4
A fresh Pt-Pd noble metal catalyst is adopted, and is obtained by the same batch production as the fresh Pt-Pd noble metal catalyst before the inactivation of the inactivated Pt-Pd noble metal catalyst in the example 3;
preparing 2.0mol/L potassium borohydride aqueous solution, keeping the temperature to 25 ℃, putting the fresh Pt-Pd noble metal catalyst into the aqueous solution, wherein the mass ratio of the total mass of Pt and Pd to the mass of potassium borohydride is 1: 1200; carrying out reaction for 4h under the ultrasonic condition; then repeatedly cleaning the mixture for more than 3 times by using deionized water to ensure that no potassium borohydride remains on the surface of the prepared material; drying in a 120 ℃ oven for 8h at the heating rate of 2 ℃/min to obtain the activated Pt-Pd noble metal catalyst.
Example 5
Compared with example 3, the difference is only that the concentration of the potassium borohydride aqueous solution is 1mol/L, and other parameter conditions are the same.
Example 6
Compared with example 3, the difference is only that the concentration of the potassium borohydride aqueous solution is 3mol/L, and other parameter conditions are the same.
Comparative example 1
The same procedure was used to deactivate the Pt-Ru noble metal catalyst of example 1.
Comparative example 2
A fresh Pt-Ru noble metal catalyst was produced in the same batch as the fresh Pt-Ru noble metal catalyst from example 1 prior to deactivation of the deactivated Pt-Ru noble metal catalyst.
Comparative example 3
Selecting the deactivated Pt-Ru noble metal catalyst in the example 1, placing the catalyst in a horizontal tubular furnace, heating to 220 ℃, introducing hydrogen, and keeping the gas-phase space velocity of the hydrogen at 600 hours-1(volume) treating the deactivated catalyst for 48h to obtain the regenerated Pt-Ru noble metal catalyst.
Comparative example 4
The same procedure was used to deactivate the Pt-Pd noble metal catalyst of example 3.
Comparative example 5
A fresh Pt-Pd noble metal catalyst, which was produced in the same batch as the fresh Pt-Pd noble metal catalyst before deactivation of the deactivated Pt-Pd noble metal catalyst in example 3.
Comparative example 6
Selecting the deactivated Pt-Pd noble metal catalyst in the example 3, placing the catalyst in a horizontal tubular furnace, heating to 220 ℃, and introducingThe space velocity of the hydrogen and the gas phase of the hydrogen is kept at 600 hours-1(volume) treating the deactivated catalyst for 48h to obtain the regenerated Pt-Pd noble metal catalyst.
Comparative example 7
Compared with example 3, the difference is that no potassium borohydride water solution is added, and other parameter conditions are the same.
Comparative example 8
Compared with example 3, the difference is only that the concentration of the potassium borohydride aqueous solution is 0.1mol/L, and other parameter conditions are the same.
Effect example 1
The regenerated Pt-Ru noble metal catalyst prepared in the above example 1 and comparative example 3, the deactivated Pt-Ru noble metal catalyst in the comparative example 1 and the fresh Pt-Ru noble metal catalyst in the comparative example 2 were used to catalyze the oxidation reaction of toluene in a fixed bed reactor, and the respective catalytic performances were evaluated, and FIG. 1 shows that toluene is catalyzed to be oxidized into CO in a catalytic bed layer at different temperatures2Conversion curve of the reaction. As can be seen from FIG. 1, the performance of the deactivated Pt-Ru noble metal catalyst is improved to more than 99% of that of the fresh Pt-Ru noble metal catalyst after being regenerated by the method of example 1, and the catalytic performance is remarkably improved compared with the regenerated Pt-Ru noble metal catalyst prepared in comparative example 3. The catalytic performance of the regenerated Pt-Ru noble metal catalyst prepared in example 1 is tested repeatedly by the test method, the number of times of repetition is three, and the result is shown in a stability curve map of FIG. 2; it can be seen from FIG. 2 that the regenerated Pt-Ru noble metal catalyst remained stable in all three replicates.
Effect example 2
The activated Pt-Ru noble metal catalyst prepared in example 2 and the fresh Pt-Ru noble metal catalyst in comparative example 2 were used to catalyze toluene oxidation reaction in a fixed bed reactor respectively, and the catalytic performance thereof was evaluated, and FIG. 3 shows that toluene oxidation is catalyzed to CO in a catalytic bed layer at different temperatures2Conversion curve of the reaction. FIG. 3 shows that the catalytic performance of the activated Pt-Ru noble metal catalyst prepared by activating the fresh Pt-Ru noble metal catalyst in example 2 is obviously improved.
Effect example 3
The regenerated Pt-Pd noble metal catalyst prepared in the above example 3 and the comparative example 6, the deactivated Pt-Pd noble metal catalyst in the comparative example 4, and the fresh Pt-Pd noble metal catalyst in the comparative example 5 were used to catalyze the oxidation reaction of toluene in the fixed bed reactor, respectively, and the respective catalytic performances were evaluated, and FIG. 4 shows that toluene was oxidized to CO in the catalytic bed at different temperatures2Conversion curve of the reaction. Fig. 4 shows that the performance of the deactivated Pt — Pd noble metal catalyst is improved to more than 99% by the method of example 3, and the catalytic performance is significantly improved compared to the regenerated Pt — Pd noble metal catalyst prepared in comparative example 6. The catalytic performance of the regenerated Pt-Pd noble metal catalyst prepared in example 3 is tested repeatedly by the above test method, the number of times of repetition is three, and the result is shown in the stability curve map of FIG. 5; it can be seen from fig. 5 that the regenerated Pt-Pd noble metal catalyst remained stable in all three replicates.
Effect example 4
Using the activated Pt-Pd noble metal catalyst prepared in example 4 and the fresh Pt-Pd noble metal catalyst in comparative example 5, respectively, the oxidation of toluene was catalyzed in a fixed bed reactor, and the catalytic performance was evaluated, and FIG. 6 shows the oxidation of toluene to CO in a catalytic bed at different temperatures2Curve of conversion of (a). Fig. 6 shows that the catalytic performance of the activated Pt-Pd noble metal catalyst prepared by activating the fresh Pt-Pd noble metal catalyst in example 4 is significantly improved.
Effect example 5
The regenerated Pt-Pd noble metal catalysts prepared in the above examples 3, 5-6 and comparative examples 7-8 were used to catalyze the oxidation of toluene in fixed bed reactors respectively, and the catalytic performance thereof was evaluated, and FIG. 7 shows that toluene was catalyzed and oxidized into CO in the catalytic bed at different temperatures2Curve of conversion of (a). Fig. 7 shows that, when the deactivated Pt-Pd noble metal catalyst is not treated with the aqueous solution of potassium borohydride, or when the concentration of the aqueous solution of potassium borohydride is low, the activation effect on the deactivated Pt-Pd noble metal catalyst is poor.
Effect example 6
The temperatures at which the toluene conversion rates of 10%, 50% and 90% were reached when the catalysts obtained in the above examples or comparative examples, respectively, were used to catalyze the oxidation reaction of toluene in a fixed bed reactor are shown in Table 2. Wherein, T10Representing the temperature at which 10% conversion of toluene was achieved, and similarly, T50 and T90 represent the temperature at which 50% and 90% conversion of toluene was achieved, respectively.
TABLE 2
Effect example 7
XPS plots of the samples Ru 3p of example 1, comparative example 1 and comparative example 2 were tested, see FIG. 9, for Pt element peak position versus Al2O3The method has coincidence and is not easy to judge, so that the change of the compound state of the noble metal Ru element before and after inactivation and regeneration is mainly researched. Ru is used as a main precious metal component of the catalyst, the research on surface valence states before and after inactivation has an important role in the research on the inactivation mechanism of the catalyst and the subsequent search of a regeneration strategy, and the fitting of the partial peak of the Ru 3p orbit discovers that the sub-peaks of 462.1eV and 484.3eV belong to Ru for the fresh catalyst in the comparative example 20The sub-peaks at 465.1eV and 487eV are attributed to Ruδ+For the deactivated catalyst of comparative example 1, the sub-peaks at 461.7eV and 483.9eV are ascribed to Ru0The sub-peaks at 464.1eV and 486.1eV are ascribed to Ruδ+Compared with the fresh catalyst in the comparative example 2, the 3p orbital binding energy of Ru on the deactivated catalyst has a negative shift value of about 0.4-1 eV, which shows that the interaction between Ru and the cerium-zirconium oxide carrier is weakened after the catalyst is deactivated, and the change is shown as the weakened ability of transferring electrons from Ru to the cerium-zirconium oxide carrier, so that the electron cloud density of the Ru atomic orbital on the deactivated catalyst is reduced. It can also be seen from the XPS results in Table 3 that Ru is produced after catalyst deactivation0Is partially oxidized and is partially oxidized,this is associated with the complex high temperature catalytic environment in which the catalyst is exposed to prior to deactivation. For the regenerated catalyst, the sub-peaks at 463.4eV and 485.4eV are ascribed to Ru0The sub-peaks at 465.1eV and 487eV are ascribed to Ruδ+For the deactivated catalyst, the sub-peaks at 461.7eV and 483.9eV are ascribed to Ru0The sub-peaks at 465.7eV and 487.6eV are ascribed to Ruδ+. The reduction of the 3p orbital binding energy shift of Ru compared to the deactivated catalyst indicates that the interaction of Ru with the supported cerium zirconium oxide is enhanced after catalyst regeneration. Also, it can be seen from the XPS results in Table 3 that Ru is produced after the catalyst has been regeneratedδ+Is partially reduced.
TABLE 3
Claims (10)
1. A method for activating a noble metal catalyst, comprising the steps of: reacting a noble metal catalyst with an activating agent in a solvent; wherein the activating agent is one or more of borohydride, hydrazine hydrate, formaldehyde, formic acid and glycol; the molar volume ratio of the activating agent to the solvent is 1mol/L or more.
2. The method of activating a noble metal catalyst according to claim 1, wherein the activator is a borohydride;
and/or the solvent is one or more of water, methanol, ethanol and tetrahydrofuran;
and/or the molar volume ratio of the activating agent to the solvent is more than 2 mol/L;
and/or the mass ratio of the noble metal to the activator in the noble metal catalyst is 1: (1000 to 1500);
and/or the noble metal catalyst is a fresh noble metal catalyst and/or a deactivated noble metal catalyst;
and/or the noble metal in the noble metal catalyst is one or more of Pt, Pd, Ru, Rh, Au, Ag and Ir.
3. The method for activating a noble metal catalyst according to claim 2, wherein the activating agent is sodium borohydride and/or potassium borohydride;
and/or, the solvent is water;
and/or the molar volume ratio of the activating agent to the solvent is 2-5 mol/L;
and/or the mass ratio of the noble metal to the activator in the noble metal catalyst is 1: (1200-1500);
and/or the deactivation source of the deactivated noble metal catalyst is one or more of sintering deactivation, poisoning deactivation, and carbon deposition deactivation;
and/or the noble metal in the noble metal catalyst is one or more of Pt, Pd and Ru.
4. The method for activating a noble metal catalyst according to claim 3, wherein the noble metal in the noble metal catalyst is "a mixture of Pt and Pd" or "a mixture of Pt and Ru";
when the noble metal in the noble metal catalyst is a mixture of Pt and Ru, the mass ratio of the Pt to the Ru is 1: (0.25 to 4), preferably 1: 2;
when the noble metal in the noble metal catalyst is a mixture of Pt and Pd, the mass ratio of Pt to Pd is 1: (0.25 to 4), preferably 1: 1.
5. the method for activating a noble metal catalyst according to claim 1, wherein the noble metal catalyst further comprises a catalyst support and/or a catalyst auxiliary;
preferably, the catalyst support is Mg2Al4Si5O18；
Preferably, the wall thickness of the catalyst carrier is 0.1 to 0.2mm, more preferably 0.15 to 0.18 mm;
preferably, the catalyst carrier has a shape of one or more of powder, granule, rod and honeycomb, more preferably honeycomb;
preferably, the catalytic promoter is cerium oxide and/or zirconium oxide.
6. The method of activating a noble metal catalyst according to claim 1, wherein when the noble metal catalyst is a fresh noble metal catalyst, the material obtained after the reaction is an activated noble metal catalyst;
and when the noble metal catalyst is an inactivated noble metal catalyst, the material prepared after the reaction is a regenerated noble metal catalyst.
7. The method for activating a noble metal catalyst according to any one of claims 1 to 6, wherein the reaction is carried out under ultrasonic conditions;
and/or the reaction temperature is 15-100 ℃, preferably 25-50 ℃;
and/or the reaction time is 0.5-48 h, preferably 1-4 h;
and/or the operation of the reaction is further followed by the operation of washing and/or drying.
8. The method for activating a noble metal catalyst according to claim 7, wherein the number of times of the water washing is three or more;
and/or, the drying is carried out in an oven;
and/or the temperature rise speed of the drying is 1-10 ℃/min, preferably 1-2 ℃/min;
and/or the drying temperature is 60-200 ℃, preferably 60-120 ℃;
and/or the drying time is 4-12 h, preferably 8-12 h.
9. An activated noble metal catalyst and/or a regenerated noble metal catalyst, which is produced by the method for activating a noble metal catalyst according to any one of claims 1 to 8.
10. Use of the activated noble metal catalyst and/or regenerated noble metal catalyst of claim 9 as a catalyst for catalyzing oxidation reactions of organic compounds.
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