CN115487832B - Catalyst for low-temperature propane oxidation and preparation method thereof - Google Patents
Catalyst for low-temperature propane oxidation and preparation method thereof Download PDFInfo
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- CN115487832B CN115487832B CN202211078626.5A CN202211078626A CN115487832B CN 115487832 B CN115487832 B CN 115487832B CN 202211078626 A CN202211078626 A CN 202211078626A CN 115487832 B CN115487832 B CN 115487832B
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 239000001294 propane Substances 0.000 title claims abstract description 53
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011258 core-shell material Substances 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims description 32
- 230000032683 aging Effects 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- YFVXLROHJBSEDW-UHFFFAOYSA-N 4-[(4-nitrophenyl)diazenyl]-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1N=NC(C=C1)=CC=C1NC1=CC=CC=C1 YFVXLROHJBSEDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- FUBACIUATZGHAC-UHFFFAOYSA-N oxozirconium;octahydrate;dihydrochloride Chemical compound O.O.O.O.O.O.O.O.Cl.Cl.[Zr]=O FUBACIUATZGHAC-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- 239000004809 Teflon Substances 0.000 description 13
- 229920006362 Teflon® Polymers 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 230000010718 Oxidation Activity Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000001000 micrograph Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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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
- 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
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for low-temperature propane oxidation and a preparation method thereof, wherein the carrier of the catalyst is of a core-shell structure, and the core is ZrO 2 Nano particles, wherein the shell layer is ZrOSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The active component is Pt, and the Pt load is 0.1-1.0 wt%. The preparation method comprises the steps of preparing the core-shell structure carrier and loading the active components. The catalyst of the invention has high catalytic activity on propane oxidation and good stability, and can completely convert 2000ppm propane into CO at 260 DEG C 2 And H 2 O, and the conversion remained stable for 40 hours continuously. Pt/ZrOSO of the invention 4 @ZrO 2 The catalyst Pt has the advantages of low load, low price, simple preparation and good propane purification effect, and is suitable for industrial production and application.
Description
Technical Field
The invention belongs to the fields of catalyst technology and environmental catalysis, and particularly relates to a catalyst for low-temperature propane oxidation and a preparation method thereof.
Background
With the rapid development of human society, petrochemical products are produced and used in large quantities, which causes the emission of volatile organic waste gas from industrial sources such as propane, propylene and the like to be increased, and causes more and more serious threat to the atmospheric environment and human health, so how to control and eliminate the emission of hydrocarbon from the source is one of the hot spots studied nowadays. The catalytic oxidation method has the advantages of high purification efficiency, low energy consumption, no secondary pollution and the like, and is one of the most effective methods for treating the low-carbon alkane emission, wherein the development of the catalytic oxidation catalyst with high activity and high stability is the core of the technology.
Depending on the active components of the catalytic oxidation catalyst, noble metal catalysts and metal oxide catalysts are classified, wherein the supported noble metal-based catalysts are widely used in catalytic oxidation reactions due to their good catalytic activity and stability, and the most commonly used noble metal catalysts are supported platinum catalysts among the catalytic oxidation catalysts for propane.
Patent CN105214687a discloses a preparation method of a nickel oxide supported chromium oxide composite oxide catalyst, namely, a chromium oxide precursor is deposited on a synthesized carrier nickel oxide, and the catalyst is obtained through washing, drying and roasting. The catalyst is used for catalytic oxidation of propane, the temperature for achieving complete oxidation is about 350 ℃, and the catalytic performance is relatively low.
Patent CN109821536A discloses a method for preparing a metal oxide with SnO 2 -Nb 2 O 5 The composite oxide is used as a carrier, and Pt and V are impregnated together 2 O 5 The supported platinum catalyst is prepared by being supported on a carrier, the lowest temperature of the series of catalysts for carrying out catalytic oxidation reaction on propane to reach 100% of propane conversion rate basically exceeds 300 ℃, the composition of the catalyst is complex, and the control requirement on the preparation of the catalyst is high.
Patent CN107537524A discloses a catalyst for complete oxidation of propane and a preparation method thereof, the catalyst is prepared from C-AlF 3 -SnO 2 The catalyst consists of a three-component carrier and noble metal Pt, wherein the mass percentage of C in the catalyst is 1.5%, and the mass percentage of Pt is 2%. However, the catalyst was used even at 15000h -1 When the catalyst is used under the space velocity condition, the conversion rate of propane reaching 99.9% still needs 275 ℃, and the preparation method of the catalyst is complex and difficult to realize industrial production and application.
In summary, it is still difficult to obtain a propane catalytic oxidation catalyst with high activity and high stability at present, and meanwhile, in the preparation of the catalyst, the process is complicated, and the catalyst is not suitable for the current industrial application. In addition, the high content of Pt as an active component in most catalysts limits the application of Pt-based catalysts for propane oxidation due to its high price and small reserves. Therefore, by selecting a proper carrier, the development of the Pt-based catalyst with low load, high activity and high stability has great practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a catalyst for low-temperature propane oxidation and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme: a catalyst for low-temp propane oxidization is composed of carrier with core-shell structure and ZrO 2 The nano particles are taken as cores, zrOSO 4 Is a shell; the active component is Pt, and the loading amount of the Pt is 0.1-1 wt%.
Further, zrO in the carrier 2 The particle size of the nano particles is 100-500 nm.
Further, the molar ratio of sulfur to zirconium in the carrier is 2:1-3:1.
Further, the preparation method of the carrier comprises the following steps: carrying out hydrothermal reaction on the Zr precursor and the S precursor to obtain zirconyl sulfate ZrOSO 4 Filtering, washing, drying and roasting the precipitate to obtain ZrOSO with a core-shell structure 4 @ZrO 2 A carrier.
Still further, the Zr precursor includes zirconium sulfate tetrahydrate, zirconyl nitrate hydrate, or zirconium oxychloride octahydrate.
Still further, the S precursor includes zirconium sulfate tetrahydrate, ammonium sulfate, concentrated sulfuric acid, or ammonium bisulfate.
Further, the hydrothermal aging temperature of the Zr and S precursors is 180-220 ℃, and the hydrothermal aging time of the Zr and S precursors is 6-24 hours; particle diameter and shell thickness are controlled by controlling the hydrothermal aging time, the hydrothermal aging temperature and the calcination temperature of the Zr precursor and the S precursor.
Further, the roasting temperature is 600-800 ℃.
It is another object of the present invention to provide a process for producing the above-mentioned low-temperature propaneA method for preparing an oxidized catalyst, the method comprising: immersing the carrier in the aqueous solution of Pt precursor, drying and calcining to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Further, the Pt precursor comprises H 2 PtCl 6 、Pt(NO 3 ) 2 、PtCl 4 、Pt(NH 3 ) 4 Cl 2 Or Pt (NH) 3 ) 4 (NO 3 ) 2 。
Compared with the prior art, the invention has the following advantages:
1. in the preparation process of the catalyst carrier, the hydrothermal aging temperature, the hydrothermal aging time and the roasting temperature are selected to greatly influence the crystalline phase of Zr species and the structure of the carrier. Different crystalline phases, such as monoclinic phase zirconium dioxide, tetragonal phase zirconium dioxide and zirconyl sulphate, and different sizes of carrier particles have a significant influence on the propane oxidation activity. According to the invention, through a large number of experiments, a core-shell catalyst with excellent propane oxidation catalytic performance is synthesized by taking a zirconyl sulfate crystal phase as a starting point; preferably ZrO 2 Nano particle as core, zrOSO 4 Is the component with optimal activity of the shell layer. On one hand, the oxidation-reduction performance of sulfate species and the adsorption performance of propane can be enhanced, and on the other hand, the interaction between the carrier and the active component Pt can be promoted, the chemical state of Pt can be regulated, and the propane oxidation performance of the catalyst can be further improved;
2. the carrier is prepared by a hydrothermal method, the hydrothermal aging temperature is between 180 and 220 ℃, the hydrothermal aging time is between 6 and 24 hours, a precipitate of zirconyl sulfate is formed after the hydrothermal treatment, and the obtained precipitate is washed, dried and roasted to obtain ZrOSO with a core-shell structure 4 @ZrO 2 A carrier. Immersing the carrier in the aqueous solution of active component Pt precursor, and finally drying and roasting to obtain Pt/ZrOSO 4 @ZrO 2 The catalyst is simple to prepare and easy for industrial production;
3. the catalyst has the advantages of low Pt loading amount of the active component, low price, simple preparation, good repeatability, easy mass production, low catalytic light-off temperature for propane, high catalytic oxidation activity for propane and high stability, and is suitable for industrial production and application.
Drawings
FIG. 1 is a transmission electron microscope image of a core-shell catalyst prepared by the invention.
FIG. 2 is an X-ray diffraction pattern of a core-shell catalyst prepared according to the present invention.
FIG. 3 is a Raman spectrum of the core-shell catalyst prepared by the present invention.
FIG. 4 is a graph showing the activity of the catalyst of examples 1-3 in catalyzing the oxidation of propane.
FIG. 5 is a graph showing the stability of the catalysts prepared in examples 1-3 of the present invention in catalyzing the oxidation of propane at 200 ℃.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the invention. These are all within the scope of the present invention.
The reagents used in the examples below were all commercially available; the various devices used in the examples below are all commercially available devices; the basic operations used in the examples are conventional, unless explicitly indicated, as is well known to those skilled in the art. The evaluation of the propane oxidizing activity of the catalyst was carried out in a fixed bed reactor, with a propane concentration of 2000ppm, an oxygen concentration of 20000ppm, the balance being nitrogen, and a mass space velocity of 30000 mL. G -1 ·h -1 。
Example 1
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 180deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 2 hours in aqueous solutionFinally, drying and roasting for 4 hours in an air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 2
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 3
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 220deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 4
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 6 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In aqueous solution for 2 hours, finallyDrying and roasting in air atmosphere at 450 ℃ for 4 hours to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 5
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 18 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 6
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 24 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 7
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 700deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, and finally dryingDrying and roasting for 4 hours in an air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 8
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 800deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 9
5g ZrONO 3 ·xH 2 O and 4.66g (NH) 4 ) 2 SO 4 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 10
5g ZrONO 3 ·xH 2 O and 6.99g (NH) 4 ) 2 SO 4 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The support powder was immersed at room temperature at a concentration of 2mL0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 11
5g ZrONO 3 ·xH 2 O and 4.06g NH 4 HSO 4 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 12
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.01g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Example 13
5g of Zr (SO) 4 ) 2 Dissolving in 100mL deionized water, stirring to dissolve thoroughly, transferring into 200mL Teflon lining stainless steel autoclave, aging at 200deg.C for 12 hr, cooling, filtering, washing, drying, and calcining at 600deg.C for 4 hr to obtain ZrOSO 4 @ZrO 2 A carrier. Then 2g ZrOSO was added 4 @ZrO 2 Carrier powderThe powder was immersed in 2mL of 5X 10 solution at room temperature -3 g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
Comparative example 1
5g ZrONO 3 ·xH 2 O was dissolved in 100mL of deionized water, stirred to be sufficiently dissolved, then transferred to a 200mL Teflon-lined stainless steel autoclave, aged at 200℃for 12 hours, cooled, and the obtained precipitate was filtered, washed, dried and calcined at 450℃for 4 hours to obtain tetragonal ZrO 2 A carrier. Then 2g ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/t-ZrO 2 A catalyst.
Comparative example 2
5g ZrONO 3 ·xH 2 O was dissolved in 100mL of deionized water, stirred to be sufficiently dissolved, then transferred to a 200mL Teflon-lined stainless steel autoclave, aged at 200℃for 12 hours, cooled, and the obtained precipitate was filtered, washed, dried and calcined at 600℃for 4 hours to obtain monoclinic phase ZrO 2 A carrier. Then 2g ZrO 2 The carrier powder was immersed in 2mL of the solution at room temperature at a concentration of 0.02g Pt Pt (NO) 3 ) 4 In water solution for 2 hours, finally drying and roasting for 4 hours in air atmosphere at 450 ℃ to obtain Pt/m-ZrO 2 A catalyst.
And (3) performance detection:
the catalysts obtained in examples 1 to 13 and comparative examples 1 to 2 were subjected to a propane oxidation activity test. The evaluation of the catalytic oxidation activity of propane of each catalyst was carried out in a fixed bed reactor (quartz tube, inner diameter 6 mm) at normal pressure. Catalyst mass 0.20g, propane concentration 2000ppm, oxygen concentration 20000ppm, N 2 To balance the gas, the mass space velocity was whsv=30000 ml·g -1 ·h -1 . The temperature of the catalyst bed is increased from 100 ℃ to 450 ℃ and the temperature rising rate is 2.5 ℃/min. By usingThe GC2060 gas chromatograph (Porapak-T column) detects import and export propane concentration online. The conversion of propane was calculated using the following formula: conversion= (C in -C out )/C in X 100%, where C in And C out The concentrations (ppm) of propane inlet and outlet, respectively.
The results of the catalytic propane oxidation activity of the catalysts obtained in examples 1 to 13 and comparative examples 1 to 2 are shown in Table 1 below. FIG. 4 is a graph showing the activity of the preferred catalyst of the present invention in catalyzing the oxidation of propane.
TABLE 1
| Examples | Catalyst | Pt loading/wt.% | S/Zr molar ratio | Full conversion temperature/°c |
| Example 1 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 256 |
| Example 2 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 249 |
| Example 3 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 251 |
| Example 4 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 281 |
| Example 5 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 252 |
| Example 6 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 253 |
| Example 7 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 272 |
| Example 8 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 311 |
| Example 9 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 277 |
| Example 10 | Pt/ZrOSO 4 @ZrO 2 | 1 | 3 | 286 |
| Example 11 | Pt/ZrOSO 4 @ZrO 2 | 1 | 2 | 265 |
| Example 12 | Pt/ZrOSO 4 @ZrO 2 | 0.5 | 2 | 271 |
| Example 13 | Pt/ZrOSO 4 @ZrO 2 | 0.1 | 2 | 332 |
| Comparative example 1 | Pt/t-ZrO 2 | 1 | 0 | 420 |
| Comparative example 2 | Pt/m-ZrO 2 | 1 | 0 | 397 |
In Table 1, it can be seen from examples and comparative examples 1-2 that Pt/ZrO with no sulfur elements present 2 The catalyst has relatively poor catalytic activity, wherein the catalyst is loaded on tetragonal ZrO 2 Pt/t-ZrO on 2 The full conversion temperature of the catalyst is 420 ℃ at the highest.
FIGS. 1 to 3 are respectively a transmission electron microscope, an X-ray diffraction and a Raman spectrum of the core-shell catalyst obtained in example 1, and it can be seen from the figures that the obtained catalyst has a core-shell structure, wherein the core body is ZrO 2 Nanoparticle structure with ZrOSO as shell outer layer 4 。
Comparing comparative examples 1 and 2 with each example, it can be seen in combination with Table 1 and FIG. 4 that the activity of the catalysts prepared in each example is significantly improved, wherein Pt/ZrOSO in example 2 4 @ZrO 2 The catalyst had the highest catalytic activity, and when the Pt loading was 1wt.%, the full conversion temperature of 2000ppm propane was 249℃because of the ZrO synthesized according to the present invention 2 Nanoparticles as cores with ZrOSO 4 The core-shell catalyst serving as a shell layer can enhance the oxidation-reduction performance of sulfate species and the adsorption performance of propane on one hand, and can promote the interaction between a carrier and active component Pt on the other hand, adjust the chemical state of Pt, and further improve the propane oxidation performance of the catalyst.
In examples 2 and 10, the S/Zr molar ratios were 2:1 and 3:1, respectively, and the corresponding propane full conversion temperatures were 249 and 286℃respectively, and the S/Zr molar ratio was 3:1, because too high an S content inhibited O 2 Is activated by adsorption.
In examples 2, 12 and 13, the Pt loading of the active component was 1, 0.5 and 0.1 respectively, and the corresponding propane full conversion temperatures were 249, 271 and 332 ℃, respectively, it can be seen that when the Pt loading was only 0.1%, the catalyst prepared by the present invention can still maintain high activity, and the problem of higher noble metal Pt loading in the previous study is avoided.
In general, in the preparation process of the carrier, catalysts with the same components and structures and prepared at different hydrothermal aging temperatures and hydrothermal aging times have similar propane oxidation activity, and are beneficial to industrial production and application of the catalyst.
Stability tests were performed on the high activity catalysts obtained in examples 1-3. The test conditions were similar to the activity test except that the catalyst bed temperature was always controlled to 200℃and the conversion of propane was measured every 1 hour. The propane oxidation stability of the catalysts obtained in examples 1-3 is shown in FIG. 5. It can be seen that the Pt loading is 1wt.% Pt/ZrOSO 4 @ZrO 2 The catalyst continuously reacts for 40 hours, the conversion rate of propane is still maintained at about 90%, and the catalyst has stable propane oxidation performance and practical application value.
Claims (7)
1. A catalyst for low-temp propane oxidization is composed of carrier with core-shell structure and ZrO 2 The nano particles are taken as cores, zrOSO 4 Is a shell; the active component is Pt, and the loading amount of the Pt is 0.1-1 wt%; the molar ratio of sulfur to zirconium in the carrier is 2:1-3:1; the preparation method of the carrier comprises the following steps: carrying out hydrothermal reaction on the Zr precursor and the S precursor to obtain zirconyl sulfate ZrOSO 4 Filtering, washing, drying and roasting the precipitate to obtain ZrOSO with a core-shell structure 4 @ZrO 2 The hydrothermal aging temperature of the Zr and S precursors is 180-220 ℃, and the hydrothermal aging time of the Zr and S precursors is 6-24 hours; particle diameter and shell thickness are controlled by controlling the hydrothermal aging time, the hydrothermal aging temperature and the calcination temperature of the Zr precursor and the S precursor.
2. A catalyst for the oxidation of low temperature propane according to claim 1, characterized in that ZrO in the support 2 The particle size of the nano particles is 100-500 nm.
3. A catalyst for the oxidation of low temperature propane according to claim 1, wherein the Zr precursor comprises zirconium sulfate tetrahydrate, zirconyl nitrate hydrate or zirconyl chloride octahydrate.
4. A catalyst for the oxidation of low temperature propane according to claim 1, wherein the S precursor comprises zirconium sulfate tetrahydrate, ammonium sulfate, concentrated sulfuric acid or ammonium bisulfate.
5. A catalyst for low temperature propane oxidation according to claim 1, wherein the calcination temperature is 600-800 ℃.
6. A process for preparing a catalyst for the oxidation of low temperature propane as claimed in claim 1, characterized in that it comprises: immersing the carrier in the aqueous solution of Pt precursor, drying and calcining to obtain Pt/ZrOSO 4 @ZrO 2 A catalyst.
7. The method for preparing a catalyst for low-temperature propane oxidation according to claim 6, wherein the Pt precursor comprises H 2 PtCl 6 、Pt(NO 3 ) 2 、PtCl 4 、Pt(NH 3 ) 4 Cl 2 Or Pt (NH) 3 ) 4 (NO 3 ) 2 。
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