CN114870871A - Low-temperature oxidation catalyst of solid acid supported platinum and preparation method and application thereof - Google Patents
Low-temperature oxidation catalyst of solid acid supported platinum and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000011973 solid acid Substances 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000000643 oven drying Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
The invention relates to a low-temperature oxidation catalyst of solid acid supported platinum and a preparation method thereof, wherein the catalyst is a catalyst for completely oxidizing ethyl acetate, which has low content of noble metal Pt and high catalytic performance, and can be carried out in a lower temperature range when the catalyst is used for completely oxidizing ethyl acetate, and the catalyst of the solid acid supported platinum is obviously beneficial to improving the water resistance of the catalyst.
Description
Technical Field
The invention relates to a chemical catalyst and a preparation method thereof, in particular to a low-temperature oxidation catalyst of solid acid supported platinum.
Background
With the increasing environmental problems, the control of Volatile Organic Compounds (VOCs) emission by the country is more and more important. Among the various VOCs treatment technologies, the catalytic combustion technology is increasingly regarded by the environmental protection industry as an efficient purification technology, wherein the catalyst is the key core of the catalytic combustion technology. In the VOCs system, ethyl acetate is a representative reactant in VOCs catalytic combustion and widely exists in the coating industry.
Platinum is the active component of a commonly used VOCs combustion catalyst. However, since platinum has been several times as expensive as palladium for over 30 years, industrial catalyst development efforts have focused on lower-priced palladium catalysts to replace the higher-priced platinum catalysts in order to reduce catalyst costs. However, the price of palladium is higher than that of platinum, and the price advantage of the palladium catalyst is lost. Therefore, the research on high-performance Pt catalyst is carried out, and the reduction of the catalyst cost is very important in practical application.
The selection of the carrier is very critical for developing high-performance catalytic combustion Pt catalysts. The supports currently used for supported Pt catalysts are metal oxides (Al) 2 O 3 、ZrO 2 、Ce x Zr 1-x O 2 Etc.) and molecular sieves (ZSM-5, SSZ-13, etc.). However, no patent reports that the solid acid carrier supported Pt catalyst is used for catalyzing ethyl acetate combustion, and the performance of the Pt catalyst is obviously improved. The high-efficiency ethyl acetate complete oxidation catalyst with platinum loaded by solid acid is prepared, and has the characteristics of high catalytic efficiency, simpler preparation, better stability and the like, particularly, the noble metal loading capacity in the catalyst is lower, and the catalyst is relatively low in price.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a catalyst for efficiently oxidizing ethyl acetate, which has low platinum content, high reaction activity, stable performance, and is resistant to water vapor, and a preparation method thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
a low-temp oxidizing catalyst with Pt carried by solid acid is composed of carrier (SO) and active component 4 2- /ZrO 2 In which SO 4 2- Rooted in ZrO 2 The content of the carrier is more than 0.01 mu mol/g; the active component is Pt metal with the load of SO 4 2- /ZrO 2 0.1-5 wt% of the carrier.
In a preferred embodiment of the present invention, the Pt metal loading is SO 4 2- /ZrO 2 0.5-2 wt% of the carrier. The invention can not only keep the activity of the catalyst, but also avoid the cost rise by controlling the Pt metal loading.
In a preferred embodiment of the present invention, the SO 4 2- Rooted in ZrO 2 The content of the carrier is 0.01-0.6 mu mol/g. The invention controls SO 4 2- Root content, which contributes to the activity of the catalyst.
In a preferred embodiment of the present invention, the SO 4 2- /ZrO 2 The support being formed by ZrO 2 Carrying sulfuric acid to prepare.
In a preferred embodiment of the invention, the active component noble metal Pt is loaded to SO by a platinum nitrate precursor 4 2- /ZrO 2 A carrier.
In another aspect, the present invention also relates to the above oxidation catalyst and a method for preparing the same, comprising the steps of:
(1)ZrO 2 preparation of oxides
With ZrOCO 3 The powder is roasted for 1 to 3 hours at the temperature of 600 ℃ under 400- 2 An oxide.
(2)SO 4 2- /ZrO 2 Preparation of the support
According to SO 4 2- In SO 4 2- /ZrO 2 Content in oxide, taking ZrO 2 Powder, measuring the corresponding volume of sulfuric acid solution, and adding ZrO 2 Soaking the oxide at the constant temperature of 30-40 ℃ for 8-16h, centrifuging, drying in an oven at the temperature of 80-120 ℃, and roasting at the temperature of 400-600 ℃ for 1-3 h to prepare SO 4 2- /ZrO 2 An oxide support.
(3)Pt-SO 4 2- /ZrO 2 Preparation of the catalyst
According to the Pt loading as SO 4 2- /ZrO 2 Measuring the mass of the carrier, measuring a proper amount of Pt metal precursor solution, and then adding SO 4 2- /ZrO 2 Carrier, water bath at 60-100 ℃ to evaporate water, drying in a drying oven at 80-120 ℃, and finally roasting at 400-600 ℃ for 1-3 hours to obtain Pt-SO 4 2- /ZrO 2 A catalyst.
The solid acid supported platinum low-temperature oxidation catalyst prepared by the specific preparation method is applied to the oxidation catalysis of ethyl acetate.
In another preferred embodiment of the invention, the catalytic reaction can be carried out under different reaction atmospheres (anhydrous or aqueous). Different from the traditional catalyst, the catalyst of the invention has stronger resistance to water vapor in reaction atmosphere.
In a preferred embodiment of the present invention, the conversion rate of ethyl acetate oxidation is above 99.5% in the catalytic reaction at a reaction temperature of 200 ℃ and 400 ℃.
In summary, the low-temperature oxidation catalyst of solid acid supported platinum, the preparation method and the application thereof disclosed by the invention have the following excellent effects:
in the invention, SO is used 4 2- /ZrO 2 The catalyst is a carrier, and Pt is an active component, and provides a catalyst for completely oxidizing ethyl acetate, which has low content of noble metal Pt and high catalytic performance, and a preparation method thereof. The catalyst prepared by the technical scheme can be carried out in a lower temperature range when being used for completely oxidizing ethyl acetate, and the water resistance of the catalyst is obviously improved by the solid acid supported platinum catalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a crystal phase structure diagram of low temperature oxidation catalysts of different acid loadings.
Figure 2 is a graph comparing the effect of moisture on example 4 and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings of the specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The examples do not specify particular techniques or conditions, and are to be construed in accordance with the description of the art in the literature or with the specification of the product. The reagents or apparatus used are conventional products commercially available from normal sources, not indicated by the manufacturer. The percentage concentrations stated, except where indicated, are mass fractions.
Example 1:
a preparation method of a solid acid supported platinum low-temperature oxidation catalyst comprises the following specific steps:
(1)ZrO 2 preparation of oxides
With ZrOCO 3 The powder is roasted for 2 hours at 500 ℃ to prepare ZrO 2 The oxide has a crystal phase structure shown in figure 1.
(2)0.005SO 4 2- /ZrO 2 Preparation of the support
According to SO 4 2- Supported on ZrO 2 The content of the oxide was 0.005. mu. mol/g. Weighing 2g of ZrO 2 Then adding 0.1mL of sulfuric acid solution (0.5mol/L), soaking at constant temperature of 35 ℃ for 12h, centrifuging, drying in a 100 ℃ oven for 8 h, and roasting at 500 ℃ for 2h to obtain 0.005SO 4 2- /ZrO 2 A solid acid carrier.
(3)Pt-0.005SO 4 2- /ZrO 2 Preparation of the catalyst
According to Pt loading of 0.005SO 4 2- /ZrO 2 0.5 wt% of the support, 10mL of a platinum nitrate solution (0.005g/mL, 0.05g of platinum metal) was measured, and 10g of 0.005SO was added 4 2- /ZrO 2 Carrier, evaporating water in 90 deg.C water bath, oven drying at 100 deg.C for 8 hr, and calcining at 500 deg.C for 2 hr to obtain Pt-0.005SO 4 2- /ZrO 2 The crystal phase structure of the catalyst is shown in figure 1.
(4) Testing of catalyst Performance
Catalyst activity test in solidThe method is carried out in a fixed bed micro reaction device, the catalyst is subjected to tabletting, 60-80 meshes of particles are screened out, and the particles are filled into a quartz tube with the inner diameter of 6mm, wherein the dosage of the catalyst is 100 mg. The oxidation activity of ethyl acetate is measured under the condition of no water vapor, and the reaction raw material gas consists of 0.3 percent of ethyl acetate and 2 percent of O 2 +97.7％N 2 The space velocities are 120000 mL g -1 ·h -1 The flow rate of the reaction gas is 200 mL/min -1 . The conversion of ethyl acetate at 250 ℃ reaction temperature was measured by a hydrogen flame ionization detector (FID detector) and the catalytic reaction performance is shown in Table 1.
Example 2:
a preparation method of a solid acid supported platinum low-temperature oxidation catalyst comprises the following specific steps:
(1)ZrO 2 the oxide was prepared as in example 1.
(2)0.010SO 4 2- /ZrO 2 And (3) preparing a carrier.
According to SO 4 2- Supported on ZrO 2 The content of the oxide is 0.010 mu mol/g. Weighing 2g of ZrO 2 Then adding 0.5mL of sulfuric acid solution (0.5mol/L), soaking at the constant temperature of 35 ℃ for 12h, centrifuging, drying in an oven at the temperature of 100 ℃ for 8 h, and roasting at the temperature of 500 ℃ for 2h to obtain 0.010SO 4 2- /ZrO 2 A solid acid carrier.
(3)Pt-0.010SO 4 2- /ZrO 2 Preparation of the catalyst
According to a Pt loading of 0.010SO 4 2- /ZrO 2 0.5 wt% of the support, 10mL of a platinum nitrate solution (0.005g/mL, 0.05g of platinum metal) was measured, and 10g of 0.010SO was added 4 2- /ZrO 2 Carrier, evaporating water in 90 deg.C water bath, drying in 100 deg.C oven for 8 hr, and calcining at 500 deg.C for 2 hr to obtain Pt-0.010SO 4 2- /ZrO 2 The crystal phase structure of the catalyst is shown in figure 1.
(4) The catalyst performance test was the same as in example 1, and the catalytic reaction performance is shown in Table 1.
Example 3:
a preparation method of a solid acid supported platinum low-temperature oxidation catalyst comprises the following specific steps:
(1)ZrO 2 the oxide was prepared as in example 1.
(2)0.030SO 4 2- /ZrO 2 And (3) preparing a carrier.
According to SO 4 2- Supported on ZrO 2 The content of the oxide is 0.030 mu mol/g. Weighing 2g of ZrO 2 Then adding 1.0mL of sulfuric acid solution (0.5mol/L), soaking at constant temperature of 35 ℃ for 12h, centrifuging, drying in a 100 ℃ oven for 8 h, and roasting at 500 ℃ for 2h to obtain 0.030SO 4 2- /ZrO 2 A solid acid carrier.
(3)Pt-0.030SO 4 2- /ZrO 2 Preparation of the catalyst
According to Pt loading of 0.030SO 4 2- /ZrO 2 0.5 wt% of the support, 10mL of a platinum nitrate solution (0.005g/mL, 0.05g of platinum metal) was measured, and 10g of 0.030SO was added 4 2- /ZrO 2 Carrier, evaporating water in water bath at 90 deg.C, oven drying at 100 deg.C for 8 hr, and calcining at 500 deg.C for 2 hr to obtain Pt-0.030SO 4 2- /ZrO 2 The crystal phase structure of the catalyst is shown in figure 1.
(4) The catalyst performance test was the same as in example 1, and the catalytic reaction performance is shown in Table 1.
Example 4:
a preparation method of a solid acid supported platinum low-temperature oxidation catalyst comprises the following specific steps:
(1)ZrO 2 the oxide was prepared as in example 1.
(2)0.050SO 4 2- /ZrO 2 And (3) preparing a carrier.
According to SO 4 2- Supported on ZrO 2 The content of the oxide is 0.050 mu mol/g. Weighing 2g of ZrO 2 Then adding 3.0mL of sulfuric acid solution (0.5mol/L), soaking at constant temperature of 35 ℃ for 12h, centrifuging, drying in a 100 ℃ oven for 8 h, and roasting at 500 ℃ for 2h to obtain 0.050SO 4 2- /ZrO 2 The solid acid carrier has a crystal phase structure shown in figure 1.
(3)Pt-0.050SO 4 2- /ZrO 2 Preparation of the catalyst
According to the Pt loading of 0.050SO 4 2- /ZrO 2 0.5 wt% of the carrier, 10mL of platinum nitrate solution (0.005g/mL, 0.05g of platinum metal) was measured, and 10g of 0.050SO was added 4 2- /ZrO 2 Carrier, evaporating water in 90 deg.C water bath, oven drying at 100 deg.C for 8 hr, and calcining at 500 deg.C for 2 hr to obtain Pt-0.050SO 4 2- /ZrO 2 The crystal phase structure of the catalyst is shown in figure 1.
(4) The catalyst performance test was the same as in example 1, and the catalytic reaction performance is shown in Table 1.
Example 5:
a preparation method of a solid acid supported platinum low-temperature oxidation catalyst comprises the following specific steps:
(1)ZrO 2 the oxide was prepared as in example 1.
(2)0.055SO 4 2- /ZrO 2 And (3) preparing a carrier.
According to SO 4 2- Supported on ZrO 2 The content of the oxide was 0.055. mu. mol/g. Weighing 2g of ZrO 2 Then adding 6.0mL of sulfuric acid solution (0.5mol/L), soaking at the constant temperature of 35 ℃ for 12h, then centrifuging, drying in a 100 ℃ oven for 8 h, roasting at 500 ℃ for 2h to obtain 0.055SO 4 2- /ZrO 2 A solid acid carrier.
(3)Pt-0.055SO 4 2- /ZrO 2 Preparation of the catalyst
According to Pt loading of 0.055SO 4 2- /ZrO 2 0.5 wt% of the support, 10mL of platinum nitrate solution (0.005g/mL, 0.05g of platinum metal) was measured, and 10g of 0.055SO was added 4 2- /ZrO 2 Carrier, evaporating water in 90 deg.C water bath, drying in 100 deg.C oven for 8 hr, and calcining at 500 deg.C for 2 hr to obtain Pt-0.055SO 4 2- /ZrO 2 The crystal phase structure of the catalyst is shown in figure 1.
(4) The catalyst performance test was the same as in example 1, and the catalytic reaction performance is shown in Table 1.
Example 6:
a preparation method of a solid acid supported platinum low-temperature oxidation catalyst comprises the following specific steps:
(1)ZrO 2 the oxide was prepared as in example 1.
(2)0.060SO 4 2- /ZrO 2 And (3) preparing a carrier.
According to SO 4 2- Supported on ZrO 2 The content of the oxide was 0.055. mu. mol/g. Weighing 2g of ZrO 2 Adding 12.0mL sulfuric acid solution (0.5mol/L), soaking at 35 deg.C for 12 hr, centrifuging, oven drying at 100 deg.C for 8 hr, and baking at 500 deg.C for 2 hr to obtain 0.060SO 4 2- /ZrO 2 A solid acid carrier.
(3)Pt-0.060SO 4 2- /ZrO 2 Preparation of the catalyst
According to Pt loading of 0.060SO 4 2- /ZrO 2 0.5 wt% of the carrier, 10mL of platinum nitrate solution (0.005g/mL, 0.05g of platinum metal) was measured, and 10g of 0.060SO was added 4 2- /ZrO 2 Carrier, evaporating water in 90 deg.C water bath, oven drying at 100 deg.C for 8 hr, and baking at 500 deg.C for 2 hr to obtain Pt-0.060SO 4 2- /ZrO 2 The crystal phase structure of the catalyst is shown in figure 1.
(4) The catalyst performance test was the same as in example 1, and the catalytic reaction performance is shown in Table 1.
Comparative example 1:
a preparation method of a solid acid supported platinum oxidation catalyst comprises the following specific steps:
(1)ZrO 2 preparation of the oxides is the same as in example 1
(2)Pt/ZrO 2 Preparation of the catalyst
ZrO according to Pt loading 2 0.5 wt% of the support, 10mL of a platinum nitrate solution (0.005g/mL, 0.05g of platinum metal) was measured, and 10g of ZrO was added 2 Carrier, evaporating water in water bath at 90 deg.c, stoving in 100 deg.c oven for 8 hr and roasting at 500 deg.c for 2 hr to obtain Pt/ZrO 2 Catalyst and process for preparing sameThe crystal phase structure is shown in figure 1.
(3) The catalyst performance test was the same as in example 1, and the catalytic reaction performance is shown in Table 2.
Comparative example 2:
a preparation method of a solid acid supported platinum oxidation catalyst comprises the following specific steps:
(1)ZrO 2 the preparation of the oxide was the same as in example 1;
(2)0.050SO 4 2- /ZrO 2 the preparation of the catalyst is the same as that of the catalyst in the example 4, platinum is not loaded, and the crystal phase structure of the catalyst is shown in the attached figure 1;
(3) the catalyst performance test was the same as in example 1, and the catalytic reaction performance is shown in Table 2.
Table 1: EXAMPLES catalyst conversion of Ethyl acetate at 250 deg.C
Table 2: comparative example catalyst conversion to ethyl acetate at 250 deg.C
As can be seen from FIG. 1, the samples in the examples all exhibit monoclinic phase ZrO 2 (m-ZrO 2 ) The crystalline phase, but no crystalline phase of Pt or sulfate species was observed, indicating that the Pt or sulfate loading had no effect on the overall crystalline phase structure of the catalyst. As can be seen from Table 1, the catalysts of examples 1-6 showed high oxidation activity to ethyl acetate, and the conversion rate reached more than 99.2% at the reaction temperature of 250 ℃, which indicates that the catalysts can catalyze the complete oxidation of ethyl acetate well. The catalyst of example 3 has the highest performance, and the conversion rate of ethyl acetate reaches 100% at the reaction temperature of 250 ℃. The oxidation activity of the comparative catalyst was significantly worse than that of the example catalyst, and the catalyst of comparative example 1 lacked SO 4 2- Ingredients; comparative example 2 catalyst lacked Pt activityAnd (3) components. Thus, it is shown that the catalyst composition and preparation method of the examples are advantageous for obtaining a high-performance catalyst.
In addition, SO 4 2- The components can remarkably improve the resistance of the catalyst to water vapor in reaction atmosphere (the experimental result is shown in the attached figure 2 of the specification).
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The low-temperature oxidation catalyst of solid acid supported platinum is characterized by comprising a carrier and an active component, wherein the carrier is SO 4 2- /ZrO 2 In which SO 4 2- Rooted in ZrO 2 The content of the carrier is more than 0.01 mu mol/g; the active component is Pt metal with the load of SO 4 2- /ZrO 2 0.1-5% of the carrier.
2. The solid acid supported platinum low temperature oxidation catalyst as claimed in claim 1, wherein the SO is 4 2- Rooted in ZrO 2 The content of the carrier is 0.01-0.6 mu mol/g, and the Pt metal loading is SO 4 2- /ZrO 2 0.5-2% of the carrier mass.
3. A method for preparing a solid acid supported platinum low temperature oxidation catalyst according to claim 1, comprising the steps of:
(1)ZrO 2 preparation of
Roasting zirconium carbonate powder to obtain ZrO 2 Powder;
(2)SO 4 2- /ZrO 2 preparation of the support
According to SO 4 2- In SO 4 2- /ZrO 2 The content of the oxide is that the ZrO prepared by the step (1) is weighed 2 Powdering, measuring the sulfuric acid solution with corresponding volume, and adding ZrO 2 Soaking at constant temperature, centrifuging, oven drying, and calcining to obtain SO 4 2- /ZrO 2 An oxide support;
(3)Pt-SO 4 2- /ZrO 2 preparation of the catalyst
According to the Pt loading as SO 4 2- /ZrO 2 Measuring a proper amount of Pt metal precursor solution according to the mass of the carrier, and then adding the SO prepared in the step (2) 4 2- /ZrO 2 Oxide carrier, evaporating water in water bath, drying in oven, and roasting to obtain Pt-SO 4 2- /ZrO 2 And (3) a catalyst, namely obtaining the low-temperature oxidation catalyst of the solid acid supported platinum.
4. The method for preparing a solid acid supported platinum low-temperature oxidation catalyst as claimed in claim 3, wherein the calcination temperature in the step (1) is 400-600 ℃, and the calcination time is 1-3 hours.
5. The method as claimed in claim 3, wherein in the step (2), the soaking temperature is 30-40 ℃, the soaking time is 8-16h, the drying temperature is 80-120 ℃, the calcination temperature is 400-.
6. The method as claimed in claim 3, wherein in the step (3), the water bath temperature is 60-100 ℃, the drying temperature is 80-120 ℃, the calcination temperature is 400-600 ℃, and the calcination time is 1-3 hours.
7. Use of the solid acid supported platinum low temperature oxidation catalyst of claim 1 or the solid acid supported platinum low temperature oxidation catalyst prepared by the method of claim 3 in the catalytic oxidation of ethyl acetate.
8. The use as claimed in claim 7, wherein the catalyst has a catalytic oxidation reaction temperature of 200 ℃ to 400 ℃ and a conversion rate of ethyl acetate oxidation of 99.5% or more.
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