CN114618476A - Monoatomic platinum-based catalyst, and preparation method and application thereof - Google Patents
Monoatomic platinum-based catalyst, and preparation method and application thereof Download PDFInfo
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- CN114618476A CN114618476A CN202210142284.2A CN202210142284A CN114618476A CN 114618476 A CN114618476 A CN 114618476A CN 202210142284 A CN202210142284 A CN 202210142284A CN 114618476 A CN114618476 A CN 114618476A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000001294 propane Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 239000003223 protective agent Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002779 inactivation Effects 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- 238000001889 high-resolution electron micrograph Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
-
- 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
Abstract
The invention belongs to the technical field of catalysis, and particularly relates to a monatomic platinum-based catalyst, a preparation method thereof and application thereof in a reaction for preparing propylene by directly dehydrogenating propane. Under the condition of stirring, adding a titanium oxide carrier into a mixed solution of ultrapure water and anhydrous methanol, then adding a platinum nanoparticle solution, then evaporating water by adopting a water bath heating method, and finally roasting in air to obtain the titanium oxide-loaded monatomic platinum-based catalyst. The prepared catalyst is a single-atom platinum-based catalyst, and the loading rate is 0.01-2 wt%. The catalyst prepared by the invention can be used for catalyzing the reaction of preparing propylene by propane dehydrogenation, has high-efficiency propylene selectivity, can maintain the olefin selectivity to be more than 92% during the operation period, has very good stability and carbon deposition resistance, can continuously operate for 70h under the reaction condition without obvious inactivation, and has strong development potential.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a monatomic platinum-based catalyst, a preparation method thereof and application thereof in a reaction for preparing propylene by directly dehydrogenating propane.
Background
The low-carbon alkane and the derivatives thereof are used as important raw materials for producing chemical products, and have wider application, the yield and the consumption of olefin are continuously increased in the whole world in recent years, wherein propylene is used as a second largest petroleum chemical raw material for producing polypropylene, acrylonitrile and propane oxide, and the propylene resource supply and demand gap is gradually increased along with the rapid increase of the demand of downstream products of propylene. Therefore, the propylene byproduct by means of traditional steam cracking and catalytic cracking is difficult to meet the requirement of chemical production on the propylene raw material, and other propylene yield increasing technologies are urgently needed. In recent years, with the rapid increase of the exploration of reserves of natural gas, particularly shale gas, the low-carbon alkane resource receives new attention, and the preparation of Propylene (PDH) by propane dehydrogenation is currently considered as an important production process for increasing the yield of propylene.
The most widely used catalyst in the industrial application of propane direct dehydrogenation to prepare propylene is mainly a noble metal Pt catalyst, but the Pt catalyst is easy to have serious inactivation problem due to coking and carbon deposition because the reaction needs to be carried out under high temperature, and the well-known reason is mainly the carbon deposition of the catalyst and then the high-temperature sintering of Pt nano particles. In order to improve the performance of Pt catalysts, it is generally necessary to add an auxiliary agent or select different carriers to suppress the occurrence of coking reaction, reduce the sintering of Pt particles, and improve the anti-carbon deposition ability and stability of the catalyst. The problem of carbon deposition is one of the most important subjects for researching Pt-based catalyst in propane dehydrogenation reaction. In recent years, basic research has made an important progress in improving the anti-coking performance of Pt-based catalysts, and among them, the team of professor "gunning dragon" (Nat. commun.,2018,9,4454) at tianjin university and the group of subjects taught by Sykes (Nat chem.,2018,10,325) at taffs university respectively find that Pt-M (M ═ Cu, Fe, Co, Ni, etc.) alloy monatomic catalysts have very good anti-coking performance, but still have the problems of poor thermal stability, low atom utilization rate, and the like, so it is important to develop novel anti-coking Pt-based catalysts.
Disclosure of Invention
The invention provides a platinum-based catalyst dispersed into monoatomic ions at high temperature and a preparation method thereof, wherein a carrier is titanium oxide, an active component is platinum metal, the loading rate of the active component is 0.01-2 wt%, the loading rate of noble metal is lower, and the atom utilization rate is high. The catalyst is applied to the reaction of preparing propylene by directly dehydrogenating propane, and can selectively break C-H bonds to convert propane into propylene. Meanwhile, the catalyst has very excellent anti-carbon deposition performance, can stably run for more than 70 hours, and is not obviously inactivated. In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of a monatomic platinum-based catalyst, which comprises the following steps:
1) under the condition of stirring, adding a titanium oxide carrier into a mixed solution of ultrapure water and anhydrous methanol, then adding a platinum nanoparticle solution, and continuously stirring for 12-24 hours to obtain a catalyst precursor solution, wherein the mass ratio of platinum nanoparticles to the titanium oxide carrier is 0.01-2%;
2) evaporating the catalyst precursor solution obtained in the step 1) to dryness by adopting a water bath heating method, controlling the heating temperature of the water bath to be 70-90 ℃, and then drying at the drying temperature of 60-300 ℃ for 1-24h to obtain a catalyst precursor;
3) and (3) roasting the catalyst precursor obtained in the step 2) in air for 1-24h at the roasting temperature of 400-800 ℃ to obtain the titanium oxide supported monatomic platinum-based catalyst.
Based on the above technical solution, preferably, the preparation method of the platinum nanoparticle solution in step 1) comprises: the method comprises the steps of adopting a sol method, taking polyvinylpyrrolidone as a protective agent, methanol as a solvent, taking one or more than two of chloroplatinic acid, platinum nitrate and platinum tetraammine nitrate as a platinum source, mixing and stirring uniformly, and refluxing at 110 ℃ for 3h to obtain a platinum nanoparticle solution.
Based on the above technical solution, preferably, the step 1) further includes: the titanium oxide carrier is sieved to 200-400 meshes and dried, the drying temperature is 100-300 ℃, and the drying time is 1-24 h.
Based on the above technical solution, preferably, the titania carrier in step 1) is one of an anatase type titania carrier, a rutile type titania carrier, and a composite crystalline phase P25 type titania carrier.
Based on the above technical solution, preferably, the titania carrier in step 1) is a nano-grade anatase titania carrier.
Based on the above technical solution, preferably, in the step 2), the drying temperature is preferably 100-.
Based on the above technical solution, preferably, in the step 3), the calcination temperature is preferably 400-600 ℃, and the calcination time is preferably 2-8 h.
The invention also provides a monoatomic platinum-based catalyst prepared by the preparation method.
Based on the technical scheme, the platinum metal in the catalyst is dispersed on the titanium oxide carrier in a single atom form, and the loading rate is 0.01-2 wt%, and preferably 0.05-1 wt%.
The invention further provides an application of the catalyst in catalyzing the reaction of directly dehydrogenating propane to prepare propylene.
Based on the technical scheme, preferably, the reaction gas is a mixed gas of propane and hydrogen, the balance gas is an inert gas, the total flow of the gas is 50-100ml/min, and the mass space velocity is 0.5-10h-1Preferably 2-6h-1The reaction pressure is 0.1-1MPa, the reaction temperature is 400-600 ℃, and the preferable temperature is 550-600 ℃.
Based on the technical scheme, preferably, the balance gas is helium or nitrogen atmosphere.
The invention has the beneficial effects that:
compared with other prior art, the preparation method has simple flow and easy operation, disperses the active component platinum nano particles into isolated platinum single atoms through simple high-temperature roasting, has lower load rate and high utilization rate of metal atoms, can simultaneously catalyze propane dehydrogenation to prepare propylene with high selectivity under relatively mild conditions, can stably run for 70 hours for a long time under reaction conditions without obvious inactivation, and shows excellent carbon deposition resistance.
Drawings
FIG. 1 is an electron micrograph of the C-AT catalyst prepared in example 1 before calcination;
FIG. 2 is a high-resolution electron micrograph of the C-AT catalyst prepared in example 1 after calcination;
FIG. 3 is a CO adsorption Fourier transform diffuse reflection infrared spectrum of the C-AT catalyst prepared in example 1;
FIG. 4 is a high resolution electron micrograph of the C-AT catalyst prepared in example 1 after the C-AT catalyst is used for catalyzing the reaction of direct dehydrogenation of propane to propylene for 70 hours;
FIG. 5 is a graph showing the activity of the C-AT catalyst prepared in example 1 for catalyzing the direct dehydrogenation of propane to propylene AT 580 deg.C under normal pressure as a function of time.
Detailed Description
The present invention will be described in detail with reference to specific examples, which are not intended to limit the scope of the present invention. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
Example 1
The preparation method of the platinum-based catalyst loaded by the anatase titanium oxide carrier AT with chloroplatinic acid as a platinum source comprises the following steps:
(1) adopting a sol method, taking polyvinylpyrrolidone as a protective agent, methanol as a solvent and chloroplatinic acid as a platinum source, mixing and stirring uniformly, and refluxing at 110 ℃ for 3h to obtain a platinum nanoparticle precursor solution;
(2) under the condition of stirring, adding 1g of anatase titanium oxide carrier AT into a mixed solution of 4ml of ultrapure water and 36ml of anhydrous methanol, adding 4ml of 0.72mmol/L platinum nanoparticle precursor solution, continuously stirring for 16h, heating in a 70 ℃ water bath to evaporate the solvent to dryness, drying AT 120 ℃ for 4h, finally roasting AT 450 ℃ in the air for 4h, wherein the heating rate is 10 ℃/min, naturally cooling, and taking out a sample, and marking as C-AT.
According to the characterization of electron microscope test and CO adsorption Fourier transform diffuse reflection infrared test, most of active component platinum in the prepared CAT-C450 catalyst is dispersed in a monatomic form after roasting treatment, and the conversion from platinum nanoparticles to single platinum atoms is realized. FIG. 1 is an electron micrograph of the C-AT catalyst prepared in example 1 before calcination, and it can be seen that before high-temperature calcination, platinum on the catalyst exists mainly in the form of nanoparticles with a size of 2-3 nm; FIG. 2 is a high resolution electron micrograph of the C-AT catalyst prepared in example 1 after being calcined AT 450 ℃ for 4 hours, and it can be seen that most of the platinum is highly dispersed on the surface of the carrier in the form of single atom after being calcined AT 450 ℃ for 4 hours, indicating that the catalyst undergoes a process of dispersing the platinum nanoparticles into single platinum atom after being calcined AT high temperature; FIG. 3 is a Fourier transform diffuse reflection infrared spectrum of CO adsorption measured after the C-AT catalyst prepared in example 1 is calcined AT 450 ℃ for 4 hours, and it can be seen that the adsorption peak of CO on a single platinum atom appears on the catalyst after the high-temperature calcination treatment.
Example 2
The preparation method of the platinum-based catalyst loaded by the anatase titanium oxide carrier AT with platinum nitrate as a platinum source comprises the following steps:
(1) adopting a sol method, taking polyvinylpyrrolidone as a protective agent, methanol as a solvent and platinum nitrate as a platinum source, mixing and stirring uniformly, and refluxing at 110 ℃ for 3h to obtain a platinum nanoparticle precursor solution;
(2) under the condition of stirring, adding 1.5g of anatase titanium oxide carrier AT into a mixed solution of 6ml of ultrapure water and 54ml of anhydrous methanol, adding 5ml of 0.81mmol/L platinum nanoparticle precursor solution, continuously stirring for 20 hours, heating by using a water bath AT 80 ℃ to evaporate the solvent, drying AT a drying temperature of 120 ℃ for 4 hours, roasting AT 450 ℃ in air for 4 hours AT a heating rate of 10 ℃/min, naturally cooling, and taking out a sample, wherein the sample is marked as N-AT.
Example 3
The preparation method of the anatase titanium oxide AT-loaded platinum-based catalyst taking platinum tetraammine nitrate as a platinum source comprises the following steps:
(1) adopting a sol method, taking polyvinylpyrrolidone as a protective agent, methanol as a solvent and platinum tetraammine nitrate as a platinum source, mixing and stirring uniformly, and refluxing at 110 ℃ for 3h to obtain a platinum nanoparticle precursor solution;
(2) adding 1.5g of anatase titanium oxide carrier AT into a mixed solution of 6ml of ultrapure water and 54ml of anhydrous methanol under the condition of stirring, adding 6ml of 0.71mmol/L platinum nanoparticle precursor solution, continuously stirring for 20 hours, heating by adopting a water bath AT 80 ℃ to evaporate the solvent, drying AT the drying temperature of 120 ℃ for 4 hours, roasting AT the temperature of 450 ℃ in the air for 4 hours AT the heating rate of 10 ℃/min, naturally cooling, and taking out a sample, wherein the sample is marked as T-AT.
Example 4
The preparation method of the rutile type titanium oxide carrier RT-loaded platinum-based catalyst taking chloroplatinic acid as a platinum source comprises the following steps:
(1) adopting a sol method, taking polyvinylpyrrolidone as a protective agent, methanol as a solvent and chloroplatinic acid as a platinum source, mixing and stirring uniformly, and refluxing at 110 ℃ for 3h to obtain a platinum nanoparticle precursor solution;
(2) under the condition of stirring, adding 1g of rutile titanium oxide carrier RT into a mixed solution of 4ml of ultrapure water and 36ml of anhydrous methanol, adding 4ml of 0.72mmol/L platinum nanoparticle precursor solution, continuously stirring for 24 hours, heating by adopting a water bath at 80 ℃ to evaporate the solvent to dryness, drying at a drying temperature of 120 ℃ for 4 hours, roasting at 450 ℃ in the air for 4 hours at a heating rate of 10 ℃/min, naturally cooling, and taking out a sample, and recording as C-RT.
Example 5
The preparation method of the composite phase P25 type titanium oxide carrier PT-loaded platinum-based catalyst with chloroplatinic acid as a platinum source comprises the following steps:
(1) adopting a sol method, taking polyvinylpyrrolidone as a protective agent, methanol as a solvent and chloroplatinic acid as a platinum source, mixing and stirring uniformly, and refluxing at 110 ℃ for 3h to obtain a platinum nanoparticle precursor solution;
(2) adding a 1g P25 type titanium oxide carrier PT into a mixed solution of 4ml of ultrapure water and 36ml of anhydrous methanol under the condition of stirring, adding 4ml of 0.72mmol/L platinum nanoparticle precursor solution, continuously stirring for 24 hours, heating by adopting a water bath at 80 ℃ to evaporate the solvent to dryness, drying at a drying temperature of 120 ℃ for 4 hours, roasting at 450 ℃ in air for 4 hours at a heating rate of 10 ℃/min, naturally cooling, and taking out a sample, wherein the sample is marked as C-PT.
Example 6
The catalysts of examples 1-5 above were tested for their catalytic performance in the dehydrogenation of propane to propylene.
Loading 300mg of catalyst into a quartz glass reaction tube by adopting a fixed bed reactor, reducing for 1.5h in a hydrogen/nitrogen mixed atmosphere at 550 ℃, then reacting at the normal pressure of 550 ℃ and 600 ℃, taking a mixed gas of propane and hydrogen as a reaction gas, taking nitrogen as a balance gas, and taking the mass space velocity of 4h-1. Meanwhile, the stability of the catalysts described in examples 1-5 in the reaction of preparing propylene by propane dehydrogenation is tested, and the results show that after long-time reaction, the catalyst C-AT loaded on an anatase type titanium oxide carrier AT and roasted AT high temperature to disperse into single platinum atoms shows good stability and carbon deposit resistance, and has obvious reaction advantages. The reaction results are detailed in table 1:
TABLE 1
Claims (10)
1. A preparation method of a monatomic platinum-based catalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
1) under the condition of stirring, adding a titanium oxide carrier into a mixed solution of ultrapure water and anhydrous methanol, then adding a platinum nanoparticle solution, and continuously stirring for 12-24 hours to obtain a catalyst precursor solution, wherein the mass ratio of platinum nanoparticles to the titanium oxide carrier is 0.01-2%;
2) evaporating the catalyst precursor solution obtained in the step 1) to dryness by adopting a water bath heating method, controlling the heating temperature of the water bath to be 70-90 ℃, and then drying at the drying temperature of 60-300 ℃ for 1-24h to obtain a catalyst precursor;
3) and (3) roasting the catalyst precursor obtained in the step 2) in air for 1-24h at the roasting temperature of 400-800 ℃ to obtain the titanium oxide supported monatomic platinum-based catalyst.
2. The method according to claim 1, wherein the method for preparing the platinum nanoparticle solution comprises: the method comprises the steps of adopting a sol method, taking polyvinylpyrrolidone as a protective agent, methanol as a solvent, taking one or more than two of chloroplatinic acid, platinum nitrate and platinum tetraammine nitrate as a platinum source, mixing and stirring uniformly, and refluxing at 110 ℃ for 3h to obtain a platinum nanoparticle solution.
3. The method of claim 1, wherein the step 1) further comprises: the titanium oxide carrier is sieved to 200-400 meshes and dried, the drying temperature is 100-300 ℃, and the drying time is 1-24 h.
4. The production method according to claim 1, characterized in that: the titanium oxide carrier in the step 1) is one of an anatase type titanium oxide carrier, a rutile type titanium oxide carrier and a composite crystal phase P25 type titanium oxide carrier.
5. The method of claim 1, wherein: the titanium oxide carrier in the step 1) is a nano-scale anatase type titanium oxide carrier.
6. A monoatomic platinum-based catalyst prepared by the method according to any one of claims 1 to 5.
7. The catalyst of claim 6 wherein the platinum metal is dispersed as a single atom on the titania support at a loading of 0.01 to 2 wt%.
8. Use of a catalyst according to any one of claims 6 to 7 for the catalytic dehydrogenation of propane to propylene.
9. Use according to claim 8, characterized in that: the reaction gas is a mixture of propane and hydrogen, and the balance isThe gas is inert gas, the total flow rate of the gas is 50-100ml/min, and the mass space velocity is 0.5-10h-1The reaction pressure is 0.1-1MPa, and the reaction temperature is 400-600 ℃.
10. Use according to claim 9, characterized in that: the balance gas is helium or nitrogen atmosphere.
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