WO2024174698A1 - 一种抗硫中毒的催化燃烧用催化剂及其制备方法和应用 - Google Patents

一种抗硫中毒的催化燃烧用催化剂及其制备方法和应用 Download PDF

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WO2024174698A1
WO2024174698A1 PCT/CN2023/139922 CN2023139922W WO2024174698A1 WO 2024174698 A1 WO2024174698 A1 WO 2024174698A1 CN 2023139922 W CN2023139922 W CN 2023139922W WO 2024174698 A1 WO2024174698 A1 WO 2024174698A1
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catalyst
sulfur
resistant
catalytic combustion
metal
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French (fr)
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安太成
尹玉妮
彭洪根
刘宏利
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Nanchang University
Guangdong University of Technology
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Nanchang University
Guangdong University of Technology
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    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • 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
    • B01J23/005—Spinels
    • 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
    • B01J23/54—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
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention belongs to the field of waste gas treatment, and in particular relates to a catalyst for catalytic combustion resistant to sulfur poisoning, a preparation method and application thereof.
  • VOCs Volatile organic compounds
  • catalytic combustion technology has been widely used in the efficient treatment of VOCs in industrial organic waste gas due to its advantages such as low ignition temperature, low energy consumption, good low-temperature catalytic activity, high treatment efficiency, no by-product generation and catalyst recyclability.
  • high-performance catalysts are its core.
  • Precious metal catalysts have excellent catalytic activity and stability for the combustion of aliphatic hydrocarbons and aromatic hydrocarbons in VOCs.
  • precious metal resources are scarce and expensive, which leads to high prices for precious metal catalysts.
  • precious metals are easily combined with sulfides in sulfur-containing industrial organic waste gas, resulting in catalyst poisoning and decreased catalytic activity. This limits the widespread application of precious metal catalysts.
  • the prior art discloses a core-shell structure catalytic combustion catalyst and a preparation method thereof, wherein a precious metal oxide as an active component of the catalyst is encapsulated in a shell composed of SiO2 and a transition metal oxide, and the transition metal oxide in the shell is used to adsorb sulfides in industrial organic waste gas, thereby improving the anti-sulfur stability of the catalyst and also ensuring that the precious metal is reduced in loss during use.
  • the catalyst provided in the prior art has a high content of precious metals, which increases the preparation cost of the catalyst.
  • the principle that the prior art can reduce the sulfur poisoning of precious metals is that the precious metals are protected in the form of an encapsulation, but the active sites of the precious metals are not fully exposed after being encapsulated by the shell layer, and the presence of the shell layer will also hinder the mass transfer during the catalytic reaction, thereby greatly affecting the catalytic activity of the catalyst.
  • the present invention provides a method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, and uses a second metal as a "sacrificial agent" to transfer the irreversible poisoning of the precious metal during the sulfur poisoning treatment process, thereby ensuring the catalytic activity of the catalyst while reducing the amount of precious metal used.
  • Another object of the present invention is to provide a catalyst for catalytic combustion that is resistant to sulfur poisoning.
  • Another object of the present invention is to provide an application of the above-mentioned sulfur-poisoning-resistant catalytic combustion catalyst in exhaust gas treatment.
  • a method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning specifically comprising the following steps:
  • step S3 The sol or solution obtained in step S2, the catalyst carrier powder and the organic solvent are fully mixed to load the precious metal and the second metal component onto the catalyst carrier, dried and calcined to obtain a catalyst for catalytic combustion that is resistant to sulfur poisoning;
  • the second metal salt is arbitrarily selected from one or more of Cu, Zn, Co, and Fe salts;
  • the catalyst carrier is magnesium aluminum spinel.
  • the reaction method used in step S2 is a polyol reduction method.
  • the polyol first acts as an organic solvent to provide a place for the dispersion of the noble metal and the second metal ions and the reduction reaction of some ions; secondly, the polyol can act as a weak reducing agent to partially reduce the noble metal component and the second metal component to obtain single-substance nanoparticles of the noble metal and the second metal.
  • the noble metal and the second metal nanoparticles can be used as active components on the sulfur-poisoning resistant catalytic combustion catalyst prepared by the present invention, because the d orbital electrons of these two metal elements are unfilled and can form a bond with the catalytic substrate to form an active reaction intermediate.
  • step S3 The reaction method used in step S3 is wet impregnation.
  • step S3 after the sol or solution obtained in S2 is added to an organic solvent, the resulting solution system contains ions and nanoparticles of the precious metal and the second metal.
  • the catalyst carrier is added to the solution system and fully mixed, so that the nanoparticles and ions of the precious metal and the second metal can be loaded onto the catalyst carrier: firstly, this is because magnesium aluminum spinel has a high specific surface area and the resulting high adsorption, which can adsorb nanoparticles of the two metals; secondly, during the mixing process, the ions of the two metals can migrate violently with the help of the flowing liquid phase, and produce electrostatic interactions with the solid phase magnesium aluminum spinel catalyst carrier, so through wet impregnation, the precious metal and the second metal combination can be loaded onto the catalyst carrier.
  • the unit cell of magnesium-aluminum spinel is composed of O 2- densely packed octahedrons, tetrahedrons, Al 3+ in the octahedral voids, and magnesium ions Mg 2+ in the tetrahedral voids, among which O 2- can attract the positively charged noble metal and second metal ions through electrostatic attraction, and this attraction is also conducive to the generation of an active interface that promotes the change of the existence form of oxygen elements.
  • polyvinyl pyrrolidone acts as a dispersant: PVP molecules have hydrophilic ends and hydrophobic ends, so they can be used as dispersants to disperse metal nanoparticles reduced by polyols; and the hydrophobic group of PVP is quite large, and the hydrophobic carbon chains of different PVP molecules can also produce a certain electrostatic repulsion. The superposition of steric hindrance effect and charge effect can further prevent the aggregation of metal ions or particles in the system.
  • PVP can promote the formation of an active interface between the noble metal and the second metal that promotes the change of the existence form of the oxygen element:
  • PVP molecules have oxygen-containing groups and the oxygen atoms of the oxygen-containing groups carry lone pairs of electrons.
  • the lone pairs of electrons can simultaneously adsorb the positively charged noble metal and the second metal ions, and when the two metal ions are reduced to metal particles in subsequent steps, there is still an adsorption effect between the noble metal and the second metal particles by means of the lone pairs of electrons on the oxygen atoms.
  • Such adsorption allows the two metal particles to interact with each other to form an active interface, which can promote the change of the existence form of the oxygen element.
  • the above-mentioned active interface that can promote the change of the existence form of oxygen element has the function of promoting the conversion of oxygen element between the two existence forms of chemically adsorbed oxygen and lattice oxygen.
  • the noble metal and the second metal nanoparticles as active components contain a certain amount of oxygen element.
  • Lattice oxygen plays a major role in the process of catalytic combustion. When lattice oxygen participates in the reaction, the metal near the oxygen site is reduced to a lower valence state.
  • chemically adsorbed oxygen can oxidize the metal in the low valence state, and the chemically adsorbed oxygen is converted into lattice oxygen, which supplements the catalytic activity of the metal.
  • the reason why the interaction between the second metal and the noble metal can form a change that promotes the existence form of oxygen element is that the content of chemically adsorbed oxygen in the second metal is higher, and the content of lattice oxygen in the noble metal is higher.
  • the sulfur-poisoning-resistant catalyst provided by the present invention loaded with two active components, the noble metal and the second metal has a lower oxygen desorption temperature than the catalyst with only the noble metal as the active component, that is, oxygen can be desorbed from the catalyst at a lower temperature.
  • the chemical state of the catalyst The ratio of chemically adsorbed oxygen to lattice oxygen also increases with the addition of the second metal.
  • the ratio of the amount of the precious metal element in the precious metal salt solution in step S2 to the amount of the second metal element in the second metal salt solution is limited to (0.1-9):1, firstly to maximize the role of the second metal as a "sacrificial agent".
  • the thermal decomposition temperature of the second metal sulfate is higher than that of the precious metal sulfate, and correspondingly, the thermal stability of the second metal sulfate is also higher, and the tendency of the sulfide to react with the second metal is greater, so the second metal can protect the precious metal from sulfur poisoning.
  • controlling the amount of the precious metal and the second metal component within the above range can reduce the amount of precious metal while ensuring the catalytic activity of the catalyst, thereby controlling the catalyst preparation cost.
  • the second metal salt is limited to one or more of Cu, Zn, Co, and Fe salts, firstly because these four second metals, compared with precious metals, are more likely to combine with sulfides in industrial organic waste gas to form sulfates, protecting the precious metals from being poisoned by sulfides.
  • the catalyst for catalytic combustion that is resistant to sulfur poisoning and constructed by using these four second metal elements and precious metals can make the performance of the catalyst in catalyzing VOCs combustion almost the same as that of the catalyst using only precious metals as active components by regulating the ratio between the second metal element and the precious metal element.
  • Magnesium aluminum spinel is used as a carrier of a catalyst for catalytic combustion that is resistant to sulfur poisoning because magnesium aluminum spinel has a high specific surface area and the O 2- in its crystal lattice can attract positively charged precious metal and second metal ions through electrostatic attraction.
  • the noble metal salt in step S1 is arbitrarily selected from one or more of Pt, Pd, Ru, Rh, and Au salts.
  • Precious metal catalysts with silver and other precious metals as the main active components have the disadvantage of poor stability. Even when the loading amount is large (>1%), their catalytic activity is difficult to compare with other precious metals.
  • the noble metal salt and the second metal salt are tetraammine noble metal nitrate or noble metal trichloride and a second metal nitrate, respectively.
  • the reaction temperature of step S2 is 100-200°C.
  • the noble metal element in the noble metal salt solution in step S2 is The molar ratio of metal elements is (0.428 ⁇ 2.3):1.
  • the catalyst has better resistance to sulfur poisoning and the cost of the catalyst is lower.
  • the total loading amount of the noble metal and the second metal in the sulfur poisoning resistant catalyst obtained in step S3 is 0.1 wt% to 1 wt%.
  • the ratio of the total mass of the precious metal and the second metal in the sol to the mass of the catalyst carrier powder is limited to the above range because when the total loading of the two metals is 0.1% to 1%, the sulfur-poisoning-resistant catalytic combustion catalyst provided by the present invention has excellent activity and low cost.
  • the molar ratio of magnesium element to aluminum element in the magnesium-aluminum spinel is 1:(2-3).
  • the molar ratio of magnesium to aluminum in magnesium-aluminum spinel is preferred because when the magnesium-aluminum ratio in magnesium-aluminum spinel is 1:(2-3), magnesium-aluminum spinel has a higher specific surface area, which is conducive to the adsorption and dispersion of the noble metal and the second metal component.
  • the unit cell of magnesium-aluminum spinel is composed of O2- close-packed octahedrons, tetrahedrons, Al3 + in the octahedral voids, and magnesium ions Mg2 + in the tetrahedral voids
  • the molar ratio of magnesium to aluminum will affect the crystal phase composition and strength of magnesium-aluminum spinel, and the lattice defects generated in magnesium-aluminum spinel will also be affected by the ratio between magnesium and aluminum, and will ultimately affect the electron density of the two active components of the noble metal and the second metal.
  • the calcination temperature in step S3 is 200-500°C.
  • the calcination time is 2 to 5 hours.
  • the auxiliary materials added in the early stage of catalyst preparation can be decomposed more completely, chemically bound water and volatile impurities can be removed more thoroughly, and the catalyst can be activated at the same time, strengthening the interaction between the active components of the catalyst and the carrier, making it difficult for the active components to migrate or aggregate, thereby ensuring the activity of the catalyst.
  • step S3 reducing gas is introduced after calcination for reduction.
  • introducing reducing gas for reduction can further reduce part of the precious metals and the second metal elements that have not been reduced by the polyol in step S2, thereby enhancing the reduction effect and ensuring that the catalyst has a high catalytic activity.
  • the reduction temperature is 200-500°C.
  • the reduction time is 2 to 5 hours.
  • the present invention also protects a sulfur-poisoning resistant catalyst for catalytic combustion, the sulfur-poisoning resistant catalyst is composed of the above
  • the catalyst is prepared by a method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning.
  • the present invention also protects the use of the above-mentioned sulfur-poisoning resistant catalytic combustion catalyst in waste gas treatment.
  • the pollutant molecules contained in the above-mentioned waste gas may be volatile organic compounds such as methane, propane, toluene, xylene or ethyl acetate.
  • the waste gas is sulfur-containing industrial organic waste gas.
  • the catalyst for catalytic combustion that is resistant to sulfur poisoning prepared by the present invention uses a second metal as a "sacrificial agent" for the precious metal to protect the precious metal, making it difficult for the precious metal to combine with sulfides in industrial organic waste gas. Therefore, when the catalyst provided by the present invention is used to catalyze the combustion of sulfur-containing industrial organic waste gas, the excellent sulfur resistance of the catalyst can be better reflected.
  • the sulfur dioxide content in the above sulfur-containing industrial organic waste gas is 1 to 200 ppm.
  • the temperature at which the catalytic substrate combustion conversion reaches 90% is used to characterize the catalytic activity of the catalyst for catalytic combustion resistant to sulfur poisoning before and after sulfur treatment.
  • the sulfur dioxide content in the sulfur-containing industrial organic waste gas is 1 to 200 ppm
  • the catalytic activity of the catalyst for catalytic combustion resistant to sulfur poisoning provided by the present invention remains basically unchanged, all at a level below 200°C.
  • the sulfur dioxide content in the sulfur-containing industrial organic waste gas is lower than 1 ppm, the sulfide in the waste gas has no obvious poisoning effect on the precious metal, which reduces the practicality of the catalyst for catalytic combustion resistant to sulfur poisoning provided by the present invention; and when the sulfur dioxide content is higher than 200 ppm, the catalyst provided by the present invention is prone to a decrease in activity due to the combination of the precious metal and the sulfide.
  • the present invention has the following beneficial effects:
  • the present invention adopts two methods, namely, polyol reduction and wet impregnation, and uses PVP as a dispersant to load precious metals and a second metal as a "sacrificial agent" on a carrier with a high specific surface area such as magnesium aluminum spinel, and there is an active interface between the two metals that can promote the change of the existence form of the oxygen element.
  • PVP polyol reduction and wet impregnation
  • the sulfur-resistant catalytic combustion catalyst prepared by the preparation method provided by the present invention can catalyze the combustion and degradation of sulfur-containing industrial organic waste gas with a sulfur dioxide content of up to 200ppm at a relatively low temperature, and the catalytic activity is almost unchanged before and after the process of catalyzing the combustion of sulfur-containing industrial organic waste gas.
  • FIG. 1 is a catalytic activity diagram of the sulfur-poisoning-resistant catalytic combustion catalyst provided in Example 1 of the present invention and Comparative Example 1.
  • the present invention is further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form.
  • the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.
  • a method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning specifically comprising the following steps:
  • step S3 The sol obtained in step S2 and the magnesium-aluminum spinel powder are mixed with anhydrous ethanol, wherein the molar ratio of magnesium element to aluminum element in the magnesium-aluminum spinel is 1:3; the mixture is stirred at room temperature for 6 hours, and then the excess ethanol is evaporated at 80°C and dried overnight; the mixture is heated to 300°C at a rate of 2°C/min, and calcined for 3 hours to obtain a solid powder, and finally a reducing atmosphere of a mixture of H2 and Ar is introduced, and the mixture is reduced at 300°C for 3 hours to obtain a catalyst for catalytic combustion that is resistant to sulfur poisoning, wherein the total loading of platinum and iron in the obtained resistant to sulfur poisoning catalyst is 0.2wt%.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • n Pt :n Fe 0.11:1.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • n Pt :n Fe 9:1.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • n Pt :n Fe 0.428:1.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • n Pt :n Fe 2.3:1.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • the total loading amount of the noble metal and the second metal in the obtained sulfur-resistant catalyst is 0.01 wt%.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • the total loading amount of the noble metal and the second metal in the obtained sulfur-resistant catalyst is 0.1 wt%.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • the total loading amount of the noble metal and the second metal in the obtained sulfur-resistant catalyst is 1 wt%.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • a method for preparing a sulfur-poisoning resistant catalyst is different from that of Example 1 in that:
  • the molar ratio of magnesium to aluminum in magnesium-aluminum spinel is 1:2.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • n Pt :n Fe 10:1.
  • Example 1 A method for preparing a catalyst for catalytic combustion that is resistant to sulfur poisoning, which is different from Example 1 in that:
  • n Pt :n Fe 0.05:1.
  • Catalytic combustion activity test 50 mg of the sulfur-poisoning-resistant catalytic combustion catalyst provided in Examples 1 to 12 of the present invention was taken and filled into a quartz reaction tube. The temperature was controlled by a thermocouple. The temperature was increased at 2°C min -1 in the range of 50 to 500°C and then tested at a constant temperature. The reaction gas was 1000 ppm o-xylene gas obtained by bubbling and diluting o-xylene with air. The total reaction gas flow rate was controlled to be 30 mL/min and the space velocity was 36000 mLg cat. -1 h -1 . The reaction tail gas was passed into a gas chromatograph for analysis. The catalytic combustion activity of the catalyst was characterized by the temperature at which the reaction gas degradation reached 90% ( T90 ). The lower the T90 , the better the catalytic combustion activity of the catalyst.
  • Anti-sulfur poisoning performance test 50 mg of the anti-sulfur poisoning catalyst provided by Examples 1 to 12 of the present invention was taken and filled into a quartz reaction tube. After the temperature was raised to 200°C at a rate of 2°C min -1 and the temperature was kept constant, a mixed gas of 200 ppm SO 2 and 16% O 2 +N 2 was introduced for sulfidation treatment, and the mixture was maintained for 3 hours. The total mixed gas flow rate was controlled to be 50 ml/min and the space velocity was 60000 mL g cat. -1 h -1 ; then, H 2 /Ar gas flow was introduced into the catalyst after sulfidation treatment, and the catalyst was reduced at 300°C for 3 hours and then used for the catalytic combustion test of o-xylene.
  • reaction gas degradation rate (X VOCs )
  • the catalyst for catalytic combustion that is resistant to sulfur poisoning provided in Example 1 of the present invention has a temperature of 193°C for catalytic degradation of o-xylene to achieve a conversion rate of 90%.
  • the temperature required for catalytic combustion is lower, that is, the activity is higher; after being treated with sulfur-containing gas with a sulfur dioxide content of up to 200 ppm, the temperature at which the catalyst catalyzes the degradation rate of o-xylene to reach 90% remains basically unchanged, indicating that the catalyst has excellent resistance to sulfur poisoning.
  • Examples 2-5 are different catalysts obtained by keeping the total amount of active component loading unchanged at 0.2wt% and changing the ratio of the amount of precious metal to the second metal substance. It can be seen from the data of Examples 1-5 that the initial catalytic activity of the catalyst is obviously positively correlated with the change in the proportion of Pt. The higher the relative content of Pt, the better the initial catalytic activity of the catalyst for catalytic combustion that is resistant to sulfur poisoning. However, after sulfur treatment, the catalytic activity of the catalyst provided by Examples 1-5 first increases and then decreases with the relative increase of the Pt content. When the ratio of the amount of precious metal to the second metal substance in the catalyst is the preferred (0.428-2.3):1 of the present invention, the catalyst has both high catalytic activity and resistance to sulfur poisoning.
  • Examples 6-9 changed the types of the precious metal and the second metal element in Example 1.
  • the test results showed that under the same content, the Pt-Fe two-component catalytic performance was the best and also exhibited good sulfur resistance.
  • Examples 10-12 changed the loading amount of the active components in Example 1.
  • the test results showed that when the loading amount of the noble metal and the second metal was lower, the activity of the catalyst in catalyzing the combustion of o-xylene decreased (manifested as an increase in T 90 ), but when the loading amount of the active components in the catalyst was increased to 1 wt%, the effect of improving the catalytic activity of the catalyst decreased and the preparation cost of the catalyst increased.
  • Examples 13-15 changed the molar ratio of magnesium to aluminum in the catalyst carrier magnesium aluminum spinel in Example 1.
  • the magnesium aluminum ratio in the magnesium aluminum spinel is 1: (2-3) as preferred in the present invention, the T 90 of the catalyst is lower, indicating that the catalytic activity of the catalyst is higher, which is caused by the larger specific surface area of the magnesium aluminum spinel.
  • Comparative Example 1 provides a catalyst prepared by adding only a single Pt.
  • the mass fraction of Pt in the catalyst is higher than that in Example 1, so the initial catalytic activity of the catalyst is also higher, and the temperature for catalyzing the degradation of o-xylene to reach 90% is 15°C lower than that of the catalyst in Example 1.
  • the temperature for catalyzing the degradation of o-xylene to reach 90% conversion rate in the catalyst in Comparative Example 1 increases by about 20°C, the catalytic activity decreases significantly, and the anti-sulfur poisoning performance is far inferior to that of the catalyst provided in Example 1.
  • the active component cost of the catalyst in Comparative Example 1 is higher, which is not conducive to its large-scale industrial application.
  • FIG1 is a comparative curve of the catalyst activity after sulfur treatment of Example 1 and Comparative Example 1. It can be seen that the T 90 temperature of the catalyst of Example 1 (solid point curve) when catalyzing o-xylene to achieve a conversion rate of 90% is 188° C., while the T 90 temperature of the catalyst of Comparative Example 1 (hollow point curve) is 297° C., that is, after sulfur poisoning treatment, the catalytic activity of Example 1 is better than that of Comparative Example 1, indicating that Example 1 of the present invention has better sulfur resistance than the catalyst of Comparative Example 1, which explains the necessity of loading the second metal in the catalyst of the present invention.

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Abstract

本发明公开了一种抗硫中毒的催化燃烧用催化剂及其制备方法和应用，具体涉及废气处理领域。本发明所提供的抗硫中毒的催化燃烧用催化剂的制备方法，采用多元醇还原法将特定的第二金属与贵金属还原并均匀分散，并采用湿法浸渍将两种金属负载在催化剂载体上，两种金属之间能够相互依存，形成活性界面。基于第二金属硫酸盐的热稳定性更高，工业有机废气中的硫化物更易与第二金属结合，因此采用本发明所提供的制备方法制备出的抗硫中毒的催化燃烧用催化剂，其中的第二金属能够起到保护贵金属免受硫中毒的作用。除此之外，第二金属也能提供一定的催化活性，降低贵金属的用量，因此本发明所提供的制备方法能够降低催化燃烧的催化剂制备成本。

Description

一种抗硫中毒的催化燃烧用催化剂及其制备方法和应用 技术领域
本发明属于废气处理领域，具体地，涉及一种抗硫中毒的催化燃烧用催化剂及其制备方法和应用。
背景技术
工业有机废气中的挥发性有机物(VOCs)对大气环境和人体健康有着严重危害，因此去除工业有机废气中的VOCs，是大气污染防治领域的热门课题。
近年来，催化燃烧技术因其起燃温度低，能耗低，低温催化活性好，处理效率高、无副产物生成及催化剂可循环使用等一系列优点而被广泛应用于工业有机废气中VOCs的高效治理。对于催化燃烧技术而言，高性能的催化剂是其核心。贵金属催化剂对VOCs中脂肪族烃、芳香烃的燃烧具有优越的催化活性和稳定性，然而，贵金属资源稀缺、价格昂贵，这就导致贵金属催化剂价格较高；与此同时，贵金属容易与含硫工业有机废气中的硫化物结合，导致催化剂中毒，催化活性下降。这使贵金属催化剂的广泛应用受到了限制。
现有技术公开了一种核壳结构催化燃烧催化剂及其制备方法，将作为催化剂活性组分的贵金属氧化物，包裹在由SiO2与过渡金属氧化物组成的外壳中，利用外壳中的过渡金属氧化物吸附工业有机废气中的硫化物，提高了催化剂的抗硫稳定性，同时也能确保贵金属在使用过程中减少流失。然而，该现有技术中所提供的催化剂中贵金属含量较高，提高了催化剂的制备成本，同时该现有技术能够降低贵金属硫中毒的原理在于采用了包裹的形式将贵金属保护起来，但贵金属被壳层包裹后活性位点暴露不充分，同时壳层的存在也会使催化反应过程中的传质受到阻碍，从而大大影响催化剂的催化活性。
发明内容
为了解决现有技术中用于催化燃烧工业有机废气的贵金属催化剂容易产生硫中毒、但保护贵金属的手段容易影响催化剂活性的问题，本发明提供了一种抗硫中毒的催化燃烧用催化剂的制备方法，采用第二金属作为“牺牲剂”转移了在硫中毒处理过程中对贵金属的不可逆毒害，在降低贵金属用量的同时保证了催化剂的催化活性。
本发明的另一目的在于提供一种抗硫中毒的催化燃烧用催化剂。
本发明的又一目的在于提供一种上述抗硫中毒的催化燃烧用催化剂在废气处理方面的应用。
本发明上述目的，通过如下技术方案实现：
一种抗硫中毒的催化燃烧用催化剂的制备方法，具体包括如下步骤：
S1.将贵金属盐与第二金属盐分别溶于水中，得到贵金属盐溶液和第二金属盐溶液；
S2.将聚乙烯吡咯烷酮加入到多元醇中，并同时向多元醇中加入贵金属盐溶液和第二金属盐溶液进行反应，得到溶胶或溶液，贵金属盐溶液中的贵金属元素与第二金属盐溶液中第二金属元素的物质的量之比为(0.1～9)：1；
S3.将步骤S2所得溶胶或溶液、催化剂载体粉末与有机溶剂充分混合，使贵金属和第二金属组分负载到催化剂载体上，烘干，焙烧，得到抗硫中毒的催化燃烧用催化剂；
第二金属盐任意地选自Cu、Zn、Co、Fe盐中的一种或多种；
催化剂载体为镁铝尖晶石。
在上述制备方法中步骤S2采用的反应方法是多元醇还原法。在步骤S2中，多元醇首先作为一种有机溶剂为贵金属和第二金属离子的分散及部分离子的还原反应提供场所；其次，多元醇能够作为一种弱还原剂将贵金属组分和第二金属组分部分还原，得到贵金属和第二金属的单质纳米颗粒。贵金属和第二金属纳米颗粒能够作为本发明所制备得到的抗硫中毒的催化燃烧用催化剂上的活性组分，因为这两种金属元素的d轨道电子是未填满的，能够与催化底物成键、形成具有活性的反应中间体。
步骤S3采用的反应方法是湿法浸渍。在步骤S3中，将S2所得溶胶或溶液加入到有机溶剂中后，所得溶液体系中含有贵金属及第二金属的离子和纳米颗粒，与此同时，将催化剂载体加入到溶液体系中充分混合，能够将贵金属和第二金属的纳米颗粒与离子负载到催化剂载体上：这首先是由于镁铝尖晶石具有高比表面积以及由此带来的高吸附性，能够吸附两种金属的纳米颗粒；其次是由于在混合过程中两种金属的离子能够借助流动的液相剧烈迁移，与固相的镁铝尖晶石这种催化剂载体产生静电相互作用，因此通过湿法浸渍，能够使贵金属和第二金属组 分负载到催化剂载体上。之所以两种金属的离子与催化剂载体能够产生静电相互作用，是因为镁铝尖晶石单位晶胞由O2-密堆积八面体、四面体和在八面体空隙中的Al3+以及在四面体空隙中的镁离子Mg2+组成，其中O2-能够通过静电吸引带正电的贵金属和第二金属离子，且这种吸引也有利于产生促进氧元素存在形式变化的活性界面。
在步骤S2中的聚乙烯吡咯烷酮即PVP是作为分散剂来起作用的：PVP分子中具有亲水端和疏水端，因此可以被用作分散剂分散被多元醇还原的金属纳米颗粒；且PVP的疏水基团体积相当大，不同PVP分子的疏水碳链之间也能够产生一定的静电斥力，空间位阻效应和电荷效应的叠加可以进一步防止体系中的金属离子或粒子聚集。其次，PVP能够促使贵金属和第二金属之间形成促进氧元素存在形式变化的活性界面：PVP分子中具有含氧基团且含氧基团的氧原子上带有孤对电子，孤对电子可以同时吸附带正电的贵金属和第二金属离子，而当两种金属离子经过后续步骤还原成金属颗粒后，贵金属和第二金属颗粒之间仍存在着借助氧原子上的孤对电子形成的吸附作用。如此吸附作用使得两种金属颗粒之间具有相互作用，形成活性界面，该活性界面能够促进氧元素存在形式的变化。
上述能够促进氧元素存在形式变化的活性界面，其作用是促进氧元素在化学吸附氧与晶格氧这两种存在形式之间转化。在采用本发明所提供的抗硫中毒的催化燃烧用催化剂的制备方法制备得到的催化剂中，作为活性组分的贵金属和第二金属纳米颗粒中含有一定的氧元素。氧元素在金属中的存在形式有两种：分别是晶格氧和化学吸附氧，晶格氧在催化燃烧的过程中起主要作用，而当晶格氧参与反应后，氧位点附近的金属被还原为较低价态，此时化学吸附氧又能够将低价态的金属氧化，化学吸附氧被转化成为晶格氧，补充了金属的催化活性。之所以第二金属与贵金属之间的相互作用能够形成促进氧元素存在形式的变化，就是因为第二金属中的化学吸附氧含量更高，而贵金属中的晶格氧含量更高，两种金属相互作用形成界面后，当贵金属中的晶格氧被消耗时，第二金属中的化学吸附氧能够迅速通过两种金属之间的活性界面，转化为贵金属中的晶格氧。据实验测得，本发明所提供的负载有贵金属和第二金属两种活性成分的抗硫中毒催化剂，和仅由贵金属作为活性组分的催化剂相比，氧气脱附温度向低温偏移，即，氧气在更低的温度下即可从催化剂上脱附。此外根据对氧元素化学态的分析，催化剂上化 学吸附氧与晶格氧的比值也随第二金属的加入而增大。
将步骤S2中贵金属盐溶液中的贵金属元素与第二金属盐溶液中第二金属元素的物质的量之比限定为(0.1～9)：1，首先是为了最大限度地发挥第二金属作为“牺牲剂”的作用。在采用本发明所提供的抗硫中毒的催化燃烧用催化剂的制备方法制备得到的抗硫中毒的催化燃烧用催化剂中，第二金属硫酸盐的热分解温度比贵金属硫酸盐的温度更高，对应地第二金属硫酸盐的热稳定性也更高，硫化物与第二金属反应的趋势更大，所以第二金属能够起到保护贵金属防止贵金属硫中毒的作用。其次，将贵金属和第二金属组分的用量控制在上述范围内，能够在保证催化剂催化活性的同时降低贵金属用量，控制催化剂制备成本。
将第二金属盐限定为Cu、Zn、Co、Fe盐中的一种或多种，首先是因为这四种第二金属，和贵金属相比更容易与工业有机废气中的硫化物结合生成硫酸盐，保护贵金属不被硫化物毒害。除此之外，采用这四种第二金属元素与贵金属共同构建的抗硫中毒的催化燃烧用催化剂，通过调控第二金属元素与贵金属元素之间的比例，能够使催化剂催化VOCs燃烧的性能与仅用贵金属作为活性组分的催化剂相差无几。这是因为，Cu、Zn、Co、Fe四种元素具有丰富多变的价态，有利于催化剂中形成更多的氧空位，提高催化剂的催化活性；与此同时，这四种第二金属元素也有利于产生促进氧元素存在形式变化的活性界面，同样能提高所形成的抗硫中毒的催化燃烧用催化剂的催化活性。
采用镁铝尖晶石作为抗硫中毒的催化燃烧用催化剂的载体，是因为镁铝尖晶石具有较高的比表面积，且其晶格中的O2-能够通过静电吸引带正电的贵金属和第二金属离子。
优选地，步骤S1的贵金属盐任意地选自Pt、Pd、Ru、Rh、Au盐中的一种或多种。
以银等其他贵金属为主要活性组分的贵金属催化剂，存在着稳定性差的缺点，同时即便在负载量较大(>1％)的情况下，其催化活性难比拟其他贵金属。
在本发明的具体实施方式中，贵金属盐和第二金属盐分别为四氨合贵金属硝酸盐或贵金属三氯化盐以及第二金属硝酸盐。
优选地，步骤S2的反应温度为100～200℃。
优选地，步骤S2中贵金属盐溶液中的贵金属元素与第二金属盐溶液中第二 金属元素的物质的量之比为(0.428～2.3)：1。
当两种金属的比例在(0.428～2.3)：1这一范围内时催化剂的抗硫中毒性能更优，催化剂的成本也较低。
优选地，步骤S3中所得抗硫中毒催化剂中贵金属与第二金属的总负载量为0.1wt％～1wt％。
将溶胶中贵金属与第二金属的总质量与催化剂载体粉末质量的比限定在上述范围内，是因为当两种金属的总负载量为0.1％～1％时本发明所提供的抗硫中毒的催化燃烧用催化剂在具有优异的活性之余，成本也较低。
优选地，步骤S3中镁铝尖晶石中镁元素与铝元素的物质的量之比为1：(2～3)。
优选镁铝尖晶石中镁元素与铝元素的物质的量之比，是因为当镁铝尖晶石中的镁铝比为1：(2～3)时镁铝尖晶石具有更高的比表面积，有利于贵金属和第二金属组分的吸附和分散。与此同时，因为镁铝尖晶石单位晶胞由O2-密堆积八面体、四面体和在八面体空隙中的Al3+以及在四面体空隙中的镁离子Mg2+组成，所以镁元素与铝元素之间的物质的量之比会影响镁铝尖晶石的晶相组成和强度，且镁铝尖晶石中产生的晶格缺陷也会受到镁元素与铝元素之间比例的影响，并最终会影响贵金属与第二金属两种活性组分的电子密度。
优选地，步骤S3中焙烧温度为200～500℃。
优选地，焙烧时间为2～5h。
通过将焙烧的温度及时间分别控制在上述范围内，既能使在催化剂制备前期投加的辅助物料分解得更完全，更彻底地去除化学结合水和挥发性杂质，也能同时活化催化剂，加强催化剂活性组分与载体间的相互作用，使活性组分不容易迁移或聚集，保证催化剂的活性。
优选地，步骤S3中在焙烧后通入还原性气体进行还原。
在焙烧后通入还原性气体进行还原，能够使在步骤S2中未被多元醇还原的部分贵金属和第二金属元素进一步还原，强化还原效果，保证催化剂具有较高的催化活性。
更优选地，还原温度为200～500℃。
更优选地，还原时间为2～5h。
本发明还保护一种抗硫中毒的催化燃烧用催化剂，该抗硫中毒催化剂由上述 抗硫中毒的催化燃烧用催化剂的制备方法制备得到。
本发明还保护一种上述抗硫中毒的催化燃烧用催化剂在废气处理方面的应用。
在本发明的具体实施方式中，上述废气中含有的污染物分子可以是甲烷、丙烷、甲苯、二甲苯或乙酸乙酯等挥发性有机物。
优选地，上述废气为含硫的工业有机废气。
本发明所制备得到的抗硫中毒的催化燃烧用催化剂，采用第二金属作为贵金属的“牺牲剂”以保护贵金属，使贵金属不易与工业有机废气中的硫化物结合，因此将本发明所提供的催化剂用于催化含硫工业有机废气的燃烧时，更能体现催化剂的优异抗硫性能。
更优选地，上述含硫的工业有机废气中的二氧化硫含量为1～200ppm。
本发明在催化含硫工业有机废气中的二氧化硫燃烧转化时，采用催化底物燃烧转化达到90％的温度表征抗硫中毒的催化燃烧用催化剂硫处理前后的催化活性，而当含硫的工业有机废气中的二氧化硫含量为1～200ppm时，本发明所提供的抗硫中毒的催化燃烧用催化剂，催化活性基本不变，均在低于200℃的水平。含硫工业有机废气中的二氧化硫含量低于1ppm时，废气中的硫化物对贵金属的毒化作用不明显，这就使得本发明所提供的抗硫中毒的催化燃烧用催化剂实用性下降；而当二氧化硫的含量高于200ppm时，本发明所提供的催化剂容易因贵金属与硫化物结合而出现活性的下降。
和现有技术相比，本发明的有益效果在于：
本发明采用了多元醇还原和湿法浸渍两种方法，以PVP作为分散剂在镁铝尖晶石这种高比表面积的载体上负载了贵金属和作为“牺牲剂”的第二金属，且两种金属之间存在有能够促进氧元素存在形式变化的活性界面，一方面既降低了贵金属用量又保证了催化剂的催化活性，控制了催化剂制备成本，另一方面采用第二金属作为牺牲剂，转移了在硫中毒处理过程中对贵金属的不可逆毒害。采用本发明所提供的制备方法制备得到的抗硫中毒的催化燃烧用催化剂，能够在较低的温度下催化二氧化硫含量高达200ppm的含硫工业有机废气燃烧、降解，且在催化含硫工业有机废气燃烧的过程前后，催化活性几乎不变。
附图说明
图1为本发明实施例1与对比例1所提供的抗硫中毒的催化燃烧用催化剂的催化活性图。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例1
一种抗硫中毒的催化燃烧用催化剂的制备方法，具体包括如下步骤：
S1.将四氨合硝酸铂、硝酸铁分别溶于水中，各自定容配制成0.02mol/L的铂盐溶液和铁盐溶液；
S2.将0.04mol PVP加入到乙二醇中，并同时向乙二醇中加入铂盐溶液和铁盐溶液进行反应，得到溶胶，铂盐溶液中的铂元素与铁盐溶液中铁元素的物质的量之比为nPt:nFe＝5：5；
S3.将步骤S2所得溶胶、镁铝尖晶石粉末与无水乙醇混合，镁铝尖晶石中镁元素与铝元素的物质的量之比为1：3；室温下搅拌6h，随后以80℃蒸干多余乙醇并烘干过夜；然后以2℃/min升温至300℃，焙烧3h得到固体粉末，最后通入H2与Ar混合的还原性气氛，在300℃下还原3h，得到抗硫中毒的催化燃烧用催化剂，所得抗硫中毒催化剂中铂与铁的总负载量为0.2wt％。
实施例2
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S2.铂盐溶液中的铂元素与铁盐溶液中铁元素的物质的量之比为nPt:nFe＝0.11：1。
实施例3
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S2.铂盐溶液中的铂元素与铁盐溶液中铁元素的物质的量之比为nPt:nFe＝9：1。
实施例4
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S2.铂盐溶液中的铂元素与铁盐溶液中铁元素的物质的量之比为nPt:nFe＝0.428：1。
实施例5
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S2.铂盐溶液中的铂元素与铁盐溶液中铁元素的物质的量之比为nPt:nFe＝2.3：1。
实施例6
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S1.将四氨合硝酸钯、硝酸铜分别溶于水中，配制成钯盐溶液和铜盐溶液。
实施例7
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S1.将三氯化铑、硝酸钴分别溶于水中，配制成铑盐溶液和钴盐溶液。
实施例8
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S1.将三氯化钌、硝酸锌分别溶于水中，配制成钌盐溶液和锌盐溶液。
实施例9
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S1.将三氯化金、硝酸铁分别溶于水中，配制金盐溶液和铁盐溶液。
实施例10
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S3.所得抗硫中毒催化剂中贵金属与第二金属的总负载量为0.01wt％。
实施例11
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S3.所得抗硫中毒催化剂中贵金属与第二金属的总负载量为0.1wt％。
实施例12
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S3.所得抗硫中毒催化剂中贵金属与第二金属的总负载量为1wt％。
实施例13
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S3.镁铝尖晶石中镁元素与铝元素的物质的量之比为1：4。
实施例14
一种抗硫中毒催化剂的制备方法，与实施例1的不同之处在于：
S3.镁铝尖晶石中镁元素与铝元素的物质的量之比为1：2。
实施例15
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S3.镁铝尖晶石中镁元素与铝元素的物质的量之比为1：1。
对比例1
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S2.仅向乙二醇中加入铂盐溶液进行反应。
对比例2
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S2.铂盐溶液中的铂元素与铁盐溶液中铁元素的物质的量之比为nPt:nFe＝10：1。
对比例3
一种抗硫中毒的催化燃烧用催化剂的制备方法，与实施例1的不同之处在于：
S2.铂盐溶液中的铂元素与铁盐溶液中铁元素的物质的量之比为nPt:nFe＝0.05：1。
性能测试
催化燃烧活性测试：取50mg本发明实施例1～12所提供的抗硫中毒的催化燃烧用催化剂，填装至石英反应管中，采用热电偶控温，在50～500℃区间以2℃min-1升温后恒温测试；反应气体是以空气对邻二甲苯进行鼓泡并稀释得到的1000ppm邻二甲苯气体，控制总反应气流速为30mL/min，空速为36000mLgcat. -1h-1；反应尾气通入气相色谱进行分析；以反应气体降解达到90％的温度(T90)表征催化剂的催化燃烧活性，T90越低，催化剂的催化燃烧活性越好。
抗硫中毒性能测试：取50mg本发明实施例1～12所提供的抗硫中毒催化剂，填装至石英反应管中，以2℃min-1升温至200℃恒温后，通入200ppm SO2与16％O2+N2混合气体进行硫化处理，保持3h，控制总混合气体流速为50ml/min，空速为60000mLgcat. -1h-1；然后向硫化处理后的催化剂通入H2/Ar气流，于300℃还原3h后用于邻二甲苯的催化燃烧测试。
反应气体降解率(XVOCs)计算公式：
性能测试数据如下表1～2与图1所示：
表1.实施例与对比例中实验设置对比
表2.实施例与对比例中数据对比

本发明实施例1所提供的抗硫中毒的催化燃烧用催化剂，对邻二甲苯催化降解达到90％转化率的温度为193℃，相较于一般的现有技术，催化燃烧所需的温度更低，即活性更高；在经过二氧化硫高达200ppm的含硫气体处理后，该催化剂催化邻二甲苯达到90％降解率的温度基本不变，说明该催化剂具有优异的抗硫中毒的能力。
实施例2-5是保持活性组分的负载总量为0.2wt％不变，改变其中贵金属与第二金属物质的量之比得到的不同催化剂，从实施例1-5的数据可以看出，催化剂的初始催化活性明显与Pt占比的改变呈正相关，Pt的相对含量越高，抗硫中毒的催化燃烧用催化剂的初始催化活性越好，但在硫处理后，实施例1-5所提供的催化剂的催化活性随着Pt含量的相对增大而先增后减，而当催化剂中贵金属与第二金属的物质物质的量之比为本发明优选的(0.428-2.3)：1时，催化剂兼具了较高的催化活性与抗硫中毒性能。
实施例6-9改变了实施例1中的贵金属与第二金属元素种类，测试结果表明，在同样含量的情况下Pt-Fe双组分催化性能最佳，同时表现出较好的耐硫性能。
实施例10-12改变了实施例1中活性组分的负载量，测试结果表明，当贵金属与第二金属的负载量更低时，催化剂催化邻二甲苯燃烧的活性下降(表现为T90提高)，但当催化剂中活性组分的负载量提高到1wt％时，催化剂催化活性的提高效果就有所下降，且催化剂的制备成本提高。
实施例13-15改变了实施例1中催化剂载体镁铝尖晶石中镁元素与铝元素的物质的量之比。当镁铝尖晶石中的镁铝比为本发明优选的1：(2～3)时，催化剂的T90更低，说明催化剂的催化活性更高，这是因为镁铝尖晶石的比表面积更大所导致的。
对比例1作为一种极端情况，提供的是一种只添加单一的Pt制备的催化剂，在该催化剂中Pt的质量分数比实施例1中Pt的高，因此催化剂的初始催化活性也较高，催化邻二甲苯降解达到90％的温度比实施例1的催化剂低15℃，但对比例1中的催化剂在硫化处理后，催化邻二甲苯降解达到90％转化率的温度提高了约20℃，催化活性大幅下降，抗硫中毒性能远不及实施例1所提供的催化剂，同时对比例1催化剂活性组分成本更高，不利于其被大规模投入工业应用。
图1为实施例1和对比例1的硫处理后催化剂活性对比曲线，可以看出实施例1的催化剂(实心点曲线)在催化邻二甲苯达到90％转化率的T90温度为188℃，而对比例1催化剂(空心点曲线)T90温度为297℃，即在硫中毒处理后实施例1比对比例1的催化活性好，说明本发明实施例1相比较于对比例1的催化剂具有较好的抗硫性能，这就说明本发明在催化剂中负载第二金属的必要性。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种抗硫中毒的催化燃烧用催化剂的制备方法，其特征在于，具体包括如下步骤：
    S1.将贵金属盐与第二金属盐分别溶于水中，得到贵金属盐溶液和第二金属盐溶液；
    S2.将聚乙烯吡咯烷酮加入到多元醇中，并同时向多元醇中加入贵金属盐溶液和第二金属盐溶液进行反应，得到溶胶或溶液，所述贵金属盐溶液中的贵金属元素与所述第二金属盐溶液中第二金属元素的物质的量之比为(0.1～9)：1；
    S3.将步骤S2所得溶胶或溶液、催化剂载体粉末与有机溶剂充分混合，使贵金属和第二金属组分负载到催化剂载体上，焙烧，得到抗硫中毒催化剂；
    所述第二金属盐任意地选自Cu、Zn、Co、Fe盐中的一种或多种；
    所述催化剂载体为镁铝尖晶石。
  2. 如权利要求1所述抗硫中毒的催化燃烧用催化剂的制备方法，其特征在于，所述贵金属盐任意地选自Pt、Pd、Ru、Rh、Au盐中的一种或多种。
  3. 如权利要求1所述抗硫中毒的催化燃烧用催化剂的制备方法，其特征在于，所述步骤S2中所述贵金属盐溶液中的贵金属元素与所述第二金属盐溶液中第二金属元素的物质的量之比为(0.428～2.3)：1。
  4. 如权利要求1所述抗硫中毒的催化燃烧用催化剂的制备方法，其特征在于，所述步骤S3中所得抗硫中毒的催化燃烧用催化剂中贵金属与第二金属的总负载量为0.1wt％～1wt％。
  5. 如权利要求1所述抗硫中毒的催化燃烧用催化剂的制备方法，其特征在于，所述步骤S3中所述镁铝尖晶石中镁元素与铝元素的物质的量之比为1：(2～3)。
  6. 如权利要求5所述抗硫中毒的催化燃烧用催化剂的制备方法，其特征在于，所述步骤S3中焙烧温度为200～500℃。
  7. 一种抗硫中毒催化剂，其特征在于，所述抗硫中毒的催化燃烧用催化剂由权利要求1～6所述抗硫中毒的催化燃烧用催化剂的制备方法制备得到。
  8. 一种权利要求7所述抗硫中毒的催化燃烧用催化剂在废气处理方面的应用。
  9. 如权利要求8所述抗硫中毒的催化燃烧用催化剂在废气处理方面的应用， 其特征在于，所述废气为含硫的工业有机废气。
  10. 如权利要求9所述抗硫中毒的催化燃烧用催化剂在废气处理方面的应用，其特征在于，所述含硫的工业有机废气中SO2的浓度为1～200ppm。
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