CN117899861A - Propane oxidative dehydrogenation monoatomic system catalyst, preparation method thereof and propylene preparation method - Google Patents
Propane oxidative dehydrogenation monoatomic system catalyst, preparation method thereof and propylene preparation method Download PDFInfo
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- CN117899861A CN117899861A CN202410024008.5A CN202410024008A CN117899861A CN 117899861 A CN117899861 A CN 117899861A CN 202410024008 A CN202410024008 A CN 202410024008A CN 117899861 A CN117899861 A CN 117899861A
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- propane
- oxidative dehydrogenation
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 308
- 239000001294 propane Substances 0.000 title claims abstract description 154
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims description 50
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 48
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 45
- 239000002243 precursor Substances 0.000 claims description 28
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- 229910052684 Cerium Inorganic materials 0.000 claims description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 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
- 239000007788 liquid Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910052738 indium Inorganic materials 0.000 abstract description 12
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 238000013112 stability test Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 31
- 238000011156 evaluation Methods 0.000 description 28
- 238000011068 loading method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 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
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a propane oxidative dehydrogenation monoatomic system catalyst, a preparation method thereof and a propylene preparation method. The propane oxidative dehydrogenation catalyst comprises an active component and a carrier, wherein the active component is loaded on the carrier, the active component is Pt monoatoms and In monoatoms, and the carrier is alumina; the mass percentage of the active component Pt in the propane oxidative dehydrogenation catalyst is 0.1-10%; the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 1-20%. The propane oxidative dehydrogenation monoatomic system catalyst provided by the invention takes Pt and In monoatoms as active components, alumina is taken as a carrier, and after the auxiliary agent is added, the propane conversion rate and the propylene selectivity are further improved, and the catalyst has the characteristics of simple synthesis method, high propylene yield and excellent stability, and achieves the purpose of preparing propylene by catalyzing propane oxidative dehydrogenation with high conversion rate and high selectivity, and the propylene yield is not obviously reduced In a stability test of 100 hours.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a propane oxidative dehydrogenation monoatomic system catalyst, a preparation method thereof and a propylene preparation method.
Background
Propylene is a raw material for producing high-value-added chemicals such as polypropylene, and in recent years, shale gas industry rapidly rises, so that the yield of propane is improved, and profit margin and economic value are provided for the reaction of preparing propylene by dehydrogenating propane.
The direct dehydrogenation of propane to propylene has the advantage of high selectivity and is also widely applied to industry. However, the propane direct dehydrogenation process is limited by thermodynamic equilibrium, and the reaction is strongly endothermic, requiring an external large amount of heat of reaction. Thus, the reaction is usually carried out at high temperature and low pressure, and the catalyst is rapidly deactivated by carbon deposition under such reaction conditions. In contrast, oxidative Dehydrogenation (ODHP) of propane to propylene is not limited by thermodynamic equilibrium and is an exothermic reaction that can be carried out at relatively low temperatures. Meanwhile, the carbon deposition problem of the catalyst can be effectively relieved by oxygen. Accordingly, oxidative dehydrogenation of propane has gained widespread attention in academia and industry in recent years.
The propylene preparation catalyst by oxidative dehydrogenation of propane comprises various transition metal oxides such as vanadium (ACS catalyst, 2015,5,5787-5793), molybdenum (J.mol.catalyst.A, 2014,392,315), chromium (Journal of Catalysis,2017, 356:197-205) and the like, and also comprises a catalyst of which hexagonal boron nitride (h-BN) (science, 2016, 354:1570-1573) and S-1 molecular sieves are loaded with B monoatomic sites and Pt/Al 2O3 nuclear In 2O3 shell structures prepared by an atomic layer deposition method. However, the propylene yield remains uneconomical due to the presence of peroxidation to form CO x product during oxidative dehydrogenation of propane. Wherein the h-BN can obtain 14% of propylene conversion and 79% of propylene selectivity, the Pt/Al 2O3 core In 2O3 shell structure catalyst has 32% of propylene conversion and 70% of propylene selectivity, the propylene selectivity gradually decreases along with the reaction time, and the Pt and In 2O3 of the Pt/Al 2O3 core In 2O3 shell structure catalyst are both nanoparticle dispersed.
Therefore, optimizing the composition of the catalyst, optimizing the synthesis method of the catalyst, and further optimizing the structure of the catalyst, and further realizing the construction of an excellent catalyst for preparing propylene by oxidative dehydrogenation of propane, obtaining the propylene yield with economic value remains a great challenge.
Disclosure of Invention
In order to obtain the propylene yield with economic value, the invention aims to provide a propane oxidative dehydrogenation monoatomic system catalyst, a preparation method and a propylene preparation method thereof.
In a first aspect, the present invention provides a propane oxidative dehydrogenation catalyst, comprising an active component and a carrier, wherein the active component is supported on the carrier, the active component is Pt monoatoms and In monoatoms, and the carrier is alumina;
The mass percentage of the active component Pt in the propane oxidative dehydrogenation catalyst is 0.1-10%;
the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 1-20%.
In the above-mentioned propane oxidative dehydrogenation catalyst, the mass percentage of the active component Pt in the propane oxidative dehydrogenation catalyst may be specifically 3%, 5%, 1%, 10% or 0.1%.
In the above-mentioned propane oxidative dehydrogenation catalyst, the mass percentage of the active component In the propane oxidative dehydrogenation catalyst may be specifically 1% -15%, 10%, 15%, 3%, 12% or 1%.
Preferably, the mass percentage of the active component Pt In the propane oxidative dehydrogenation catalyst is 1-10%, and the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 1-15%;
More preferably, the mass percentage of the active component Pt In the propane oxidative dehydrogenation catalyst is 1-5%, and the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 3-15%;
Further preferably, the mass percentage of the active component Pt In the propane oxidative dehydrogenation catalyst is 3-5%, and the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 10-15%;
still further preferably, the mass percentage of the active component Pt In the propane oxidative dehydrogenation catalyst is 3%, and the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 10%.
In a second aspect, the present invention provides a method for preparing the propane oxidative dehydrogenation catalyst, comprising the steps of:
and adding a Pt precursor and an In precursor salt into the aqueous dispersion of alumina, and sequentially stirring, drying for the first time, roasting for the first time and reducing at different temperature sections to obtain the propane oxidative dehydrogenation catalyst.
In the preparation method of the propane oxidative dehydrogenation catalyst, the precursor of Pt is chloroplatinic acid;
the precursor of In is indium nitrate;
the concentration of the alumina in the aqueous dispersion of alumina may be 0.002 to 0.2g/mL, specifically 0.02g/mL;
the temperature of the first drying can be 50-80 ℃, specifically 80 ℃, and the time can be 8-12 hours, specifically 10 hours;
The temperature of the first roasting can be 500-750 ℃, specifically 550 ℃, and the time can be 1-3 hours, specifically 2 hours;
The first firing is performed in an air atmosphere;
The reduction is carried out in 10% H 2 atmosphere at 150 deg.C, 200 deg.C, 250 deg.C and 490 deg.C for 0.5-2 hours.
In a third aspect, the invention provides a propane oxidative dehydrogenation catalyst, which comprises an active component, a carrier and an auxiliary agent, wherein the active component and the auxiliary agent are loaded on the carrier, the active component is Pt monoatoms and In monoatoms, the auxiliary agent is one or more of gold, silver, palladium, ruthenium, cobalt, cerium and copper, and the carrier is alumina;
The mass percentage of the active component Pt in the propane oxidative dehydrogenation catalyst is 0.1-10%;
the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 1% -20%;
The mass percentage of each auxiliary agent in the propane oxidative dehydrogenation catalyst is 0.03-8%.
In the above-mentioned oxidative dehydrogenation catalyst for propane, the mass percentage of each of the auxiliary agents in the oxidative dehydrogenation catalyst for propane may be specifically 0.03%, 0.1%, 0.5%, 1%, 3%, 5%, 8%, and, as an example of palladium auxiliary agent, 0.03% to 8%, 0.1% to 8%, more preferably 0.5% to 1%, and still more preferably 1%.
In the above-mentioned propane oxidative dehydrogenation catalyst, the auxiliary agent may include a first auxiliary agent and a second auxiliary agent, and is any one of the following:
1) The first auxiliary agent is palladium, and the second auxiliary agent is any one of ruthenium, cobalt, cerium and copper;
2) The first auxiliary agent is cobalt, and the second auxiliary agent is cerium.
In the technical scheme 1), the mass percentage of the first auxiliary agent is 1% -5% (such as 1%, 3% or 5%), and the mass percentage of the second auxiliary agent is 1% -8%. Preferably, the mass percent of the first auxiliary agent is 3% -5%, and the mass percent of the second auxiliary agent is 3% -5%. More preferably, the mass percentage of the first auxiliary agent is 3%, and the mass percentage of the second auxiliary agent is 3%.
In the technical scheme 2), the mass percentage of cobalt is 3% -8% (such as 3%, 5% or 8%), and the mass percentage of cerium is 1% -8% (such as 1%, 3%, 5%, 7% or 8%). Preferably, the mass percentage of cobalt is 3% -8% and the mass percentage of cerium is 1% -7%. More preferably, the mass percentage of cobalt is 3% -8% and the mass percentage of cerium is 1% -5%. Further preferably, the mass percentage of cobalt is 3% -5% and the mass percentage of cerium is 1% -3%. Still more preferably, the mass percentage of cobalt is 3% and the mass percentage of cerium is 1%.
In a fourth aspect, the present invention provides a method for preparing the propane oxidative dehydrogenation catalyst, comprising the steps of:
(1) Adding a precursor of Pt and a precursor salt of In into a water dispersion liquid of alumina, and sequentially stirring, drying for the first time, roasting for the first time and reducing at different temperature sections;
(2) And immersing the product after the first roasting in an aqueous solution of a precursor of the auxiliary agent, and sequentially performing second drying and second roasting to obtain the propane oxidative dehydrogenation catalyst.
In the preparation method, the precursor of Pt is chloroplatinic acid;
the precursor of In is indium nitrate;
the concentration of the alumina in the aqueous dispersion of alumina may be 0.002 to 0.2g/mL, specifically 0.02g/mL;
the temperature of the first drying can be 50-80 ℃, specifically 80 ℃, and the time can be 8-12 hours, specifically 10 hours;
The temperature of the first roasting can be 500-750 ℃, specifically 550 ℃, and the time can be 1-3 hours, specifically 2 hours;
The first firing is performed in an air atmosphere;
The reduction is carried out in 10% H 2 atmosphere at 150 ℃, 200 ℃, 250 ℃ and 490 ℃ for 0.5-2 hours respectively;
The precursor of the auxiliary agent is chloride, nitrate, sulfate or acetate of the auxiliary agent;
the concentration of the precursor of the auxiliary agent in the aqueous solution of the precursor of the auxiliary agent may be 0.02-0.04 g/ml, in particular 0.04g/ml;
The temperature of the second drying can be 50-80 ℃, specifically 80 ℃, and the time can be 8-12 hours, specifically 10 hours;
The temperature of the second roasting can be 150-450 ℃, specifically 225 ℃, and the time can be 2-4 hours, specifically 3 hours;
the second firing is performed in an air atmosphere.
In a fifth aspect, the present invention provides a method for preparing propylene by catalytic oxidative dehydrogenation of propane, comprising the steps of:
in the presence of oxygen and diluent gas, the propane is subjected to oxidative dehydrogenation under the catalysis of the propane oxidative dehydrogenation catalyst to obtain propylene.
In the method, the propane oxidative dehydrogenation catalyst is heated to the oxidative dehydrogenation temperature in a reducing atmosphere;
the reducing atmosphere consists of 1-10% (such as 10%) of reducing gas by volume percentage and balance gas by volume percentage;
The balance gas is nitrogen or argon;
The reducing gas is hydrogen or carbon monoxide.
In the above method, the volume percentage of the propane in the reaction gas consisting of the propane, the oxygen and the diluent gas is 3% -20%, such as 4.3%;
the oxygen accounts for 1.5-10% of the volume of the reaction gas consisting of the propane, the oxygen and the diluent gas, such as 2.15%;
The dilution gas is nitrogen, helium or argon;
The temperature of the oxidative dehydrogenation is 400-600 ℃, such as 490 ℃;
The reaction hourly space velocity of the propane oxidative dehydrogenation catalyst is from 42 to 60L/g/h, such as 42L/g/h, based on the reaction gas per gram of catalyst passed per unit time.
The invention has the following benefits:
Compared with the prior art, the invention has the following advantages: firstly, the preparation method is simple, the synthesis period is short, the high-efficiency catalyst can be obtained by stirring and roasting, and the synthesis efficiency is extremely high; secondly, the propylene yield of the transition metal oxide and boron nitride catalyst exceeds 500 ℃ at the reaction temperature of 490 ℃, so that the purpose of preparing propylene by catalyzing the oxidative dehydrogenation of propane with high conversion rate and high selectivity is realized; thirdly, the material has excellent stability, and the propylene yield is not obviously reduced in a stability test for 100 hours. Therefore, the catalyst has application prospect and economic value.
Drawings
Fig. 1 shows the results of the spherical aberration electron microscope characterization of Pt monoatoms and In monoatoms In example 1 of the present invention, and it can be seen that Pt monoatoms have higher brightness than In monoatoms, and Pt and In the catalyst of the present invention are both dispersed In the form of monoatoms, and are highly dispersed.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The methods used in the examples described below, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the specifications of the product. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In the following examples, the conversion and selectivity were calculated as follows:
alkane conversion (%) = [ (moles of alkane before reaction-moles of alkane after reaction)/moles of alkane before reaction ] ×100%;
product selectivity (%) = [ carbon number in product/(carbon number of alkane before reaction-carbon number of alkane after reaction) ]x100%;
product yield (%) =alkane conversion x product selectivity.
In the following examples, the reaction space-time velocity was calculated as follows:
reaction hourly space velocity = volume of reaction gas per hour (L)/catalyst mass (g).
Calcination in the following examples was carried out in air unless otherwise specified.
The conditions for the gas chromatography of propylene were as follows: the FID detector temperature was 250deg.C, hydrogen flow 40ml/min, air flow 400ml/min, and the column box was kept at 35deg.C for 2min, then raised to 85deg.C at 10deg.C/min. The flow rate of the chromatographic column is 7ml/min.
All the loadings in the examples below were theoretical loadings.
Example 1
The preparation process of the catalyst Pt-In/Al 2O3 In this example is as follows:
10g of alumina was weighed, 500ml of water was added to prepare a suspension, 2.63g of indium nitrate and 16.7ml of an aqueous solution of chloroplatinic acid (18.0 mg/ml) were added, stirred at room temperature for 10 hours, dried overnight at 80℃for 10 hours, baked at 550℃for 2 hours in a muffle furnace, and then reduced at 150℃200℃250℃and 490℃for 0.5 hours, respectively, in sequence, in a 10% H 2 atmosphere.
The catalyst prepared In this example had a mass fraction of Pt of 3% In/Al 2O3 and a mass fraction of In of 10%, denoted 3Pt-10In/Al 2O3.
0.1G of 3Pt-10In/Al 2O3 was placed In a fixed bed reactor and heated to 490℃in a 10% hydrogen atmosphere (balance nitrogen). Closing hydrogen, and introducing reaction gas, wherein the gas composition is 4.3% by volume of propane, 2.15% by volume of oxygen and the balance of nitrogen, and the reaction time-space speed is 42L/g/h. The results of the activity evaluation are shown in Table 1.
TABLE 1 example 1 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 42 |
| Propylene selectivity | 61 |
| Propylene yield | 25.6 |
Example 2
The preparation process of the catalyst Pt-In/Al 2O3 In this example is as follows:
10g of alumina was weighed, 500ml of water was added to prepare a suspension, 3.95g of indium nitrate and 27.8ml of an aqueous solution of chloroplatinic acid (18.0 mg/ml) were added, stirred at room temperature for 10 hours, dried overnight at 70℃and baked at 650℃for 3 hours in a muffle furnace, followed by reduction at 150℃200℃250℃and 490℃respectively for 0.5 hours in a 10% H 2 atmosphere.
The catalyst prepared In this example had a mass fraction of Pt of 5% In/Al 2O3 and a mass fraction of In of 15%, denoted 5Pt-15In/Al 2O3.
The material catalytic propane oxidative dehydrogenation test was consistent with example 1 and the dehydrogenation activity was evaluated as shown in table 2.
TABLE 2 example 2 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 37 |
| Propylene selectivity | 57 |
| Propylene yield | 21.1 |
Example 3
The preparation process of the catalyst Pt-In/Al 2O3 In this example is as follows:
10g of alumina was weighed, 500ml of water was added to prepare a suspension, 0.79g of indium nitrate and 5.6ml of an aqueous solution of chloroplatinic acid (18.0 mg/ml) were added, stirred at room temperature for 10 hours, dried overnight at 60℃and baked at 500℃for 1 hour in a muffle furnace, followed by reduction at 150℃200℃at 250℃and 490℃for 0.5 hour, respectively, in a 10% H 2 atmosphere.
The catalyst prepared In this example had a mass fraction of Pt of 1% In/Al 2O3 and a mass fraction of In of 3%, denoted Pt-3In/Al 2O3.
The material catalytic propane oxidative dehydrogenation test was consistent with example 1 and the activity evaluation results are shown in table 3.
TABLE 3 example 3 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 32 |
| Propylene selectivity | 51 |
| Propylene yield | 16.3 |
Example 4
The preparation process of the catalyst Pt-In/Al 2O3 In this example is as follows:
10g of alumina was weighed, 500ml of water was added to prepare a suspension, 3.16g of indium nitrate and 56ml of an aqueous solution of chloroplatinic acid (18.0 mg/ml) were added, stirred at room temperature for 10 hours, dried overnight at 60℃and baked at 500℃for 1 hour in a muffle furnace, followed by reduction at 150℃200℃250℃and 490℃for 0.5 hour, respectively, in a 10% H 2 atmosphere.
The catalyst prepared In this example had a mass fraction of Pt of 10% and a mass fraction of In of 12% In Pt-In/Al 2O3, denoted as 10Pt-12In/Al 2O3.
The material catalytic propane oxidative dehydrogenation test was consistent with example 1 and the activity evaluation results are shown in table 4.
Table 4, example 4 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 16 |
| Propylene selectivity | 52 |
| Propylene yield | 8.3 |
Example 5
The preparation process of the catalyst Pt-In/Al 2O3 In this example is as follows:
10g of alumina was weighed, 500ml of water was added to prepare a suspension, 0.26g of indium nitrate and 16.7ml of an aqueous solution of chloroplatinic acid (18.0 mg/ml) were added, stirred at room temperature for 10 hours, dried overnight at 60℃and baked at 500℃for 1 hour in a muffle furnace, followed by reduction at 150℃200℃at 250℃and 490℃for 0.5 hour, respectively, in a 10% H 2 atmosphere.
The catalyst prepared In this example had a mass fraction of Pt of 3% In/Al 2O3 and a mass fraction of In of 1%, denoted 3Pt-In/Al 2O3.
The material catalytic propane oxidative dehydrogenation test was consistent with example 1 and the activity evaluation results are shown in table 5.
TABLE 5 example 5 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 20 |
| Propylene selectivity | 42 |
| Propylene yield | 8.4 |
Comparative example 1
The preparation process of the catalyst Pt/Al 2O3 of the comparative example is as follows:
The preparation process is the same as in example 1, and only the addition of indium nitrate is omitted.
The mass fraction of Pt in the catalyst Pt/Al 2O3 prepared in this comparative example was 3%, designated 3Pt/Al 2O3.
The results of the activity evaluation are shown in Table 6.
TABLE 6 catalytic Activity of comparative example 1
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 5 |
| Propylene selectivity | 22 |
| Propylene yield | 11 |
Comparative example 2
The preparation process of the catalyst In/Al 2O3 of the comparative example is as follows:
the preparation procedure was as in example 1, omitting the addition of the aqueous solution of chloroplatinic acid.
The mass fraction of In the catalyst In/Al 2O3 prepared In this comparative example was 3%, which was designated as 10In/Al 2O3.
The results of the activity evaluation are shown in Table 7.
TABLE 7 catalytic Activity of comparative example 1
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 2 |
| Propylene selectivity | 17 |
| Propylene yield | 3.4 |
Comparative example 3
The preparation process of the catalyst Pt-In/Al 2O3 In this example is as follows:
10g of alumina was weighed, 500ml of water was added to prepare a suspension, 0.26g of indium nitrate and 0.56ml of an aqueous solution of chloroplatinic acid (18.0 mg/ml) were added, and the mixture was stirred at room temperature for 10 hours, dried overnight at 60℃and calcined in a muffle furnace at 500℃for 1 hour.
The catalyst prepared In this example had a mass fraction of Pt of 0.1% In/Al 2O3 and a mass fraction of In of 1%, denoted 0.1Pt-In/Al 2O3.
The material catalytic propane oxidative dehydrogenation test was consistent with example 1 and the activity evaluation results are shown in table 8.
Table 8, comparative example 1 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 10 |
| Propylene selectivity | 39 |
| Propylene yield | 3.9 |
Fig. 1 shows the results of the spherical aberration electron microscope characterization of Pt monoatoms and In monoatoms In example 1 of the present invention, and it can be seen that Pt monoatoms have higher brightness than In monoatoms, and Pt and In the catalyst of the present invention are both dispersed In the form of monoatoms, and are highly dispersed.
As can be seen from the above examples 1 and comparative examples 1 to 2, the catalyst of the present invention has Pt and In single atoms as active components, and the catalytic activity is greatly improved relative to the single active component.
As can be seen from the above examples 1 to 5 and comparative example 3, the mass fraction of Pt and In the catalyst directly affects the activity of the catalyst, wherein the mass percentage of Pt is preferably 1% to 10%, more preferably 1% to 5%, still more preferably 3% to 5%; the mass percentage of In is preferably 1% to 15%, more preferably 3% to 15%, and even more preferably 10% to 15%.
Example 6
The preparation process of the catalyst M/Pt-In/Al 2O3 In this example is as follows:
(1) 3Pt-10In/Al 2O3 was prepared as described In example 1.
(2) 1G of palladium nitrate was dissolved in 25ml of water as a precursor of palladium as an auxiliary. 0.4g of 3Pt-10In/Al 2O3 is weighed, 0.0065ml of palladium nitrate solution is added to enable the palladium loading amount to be 0.03%, the catalyst is dried overnight (10 hours) at 80 ℃, and the catalyst containing auxiliary palladium is obtained after roasting for 3 hours at 225 ℃ In a muffle furnace, and is recorded as 0.03Pd/3Pt-10In/Al 2O3.
The material catalytic propane oxidative dehydrogenation test was consistent with example 1 and the activity evaluation results are shown in table 9.
Table 9, example 6 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 45 |
| Propylene selectivity | 62 |
| Propylene yield | 27.9 |
Example 7
The remaining results are shown in Table 10, except that the palladium loading is 0.1% in accordance with example 6.
TABLE 10 example 7 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 45 |
| Propylene selectivity | 63 |
| Propylene yield | 28.4 |
Example 8
The remaining results are shown in Table 11, except that the palladium loading is 0.5%, in accordance with example 6.
Table 11, example 8 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 47 |
| Propylene selectivity | 63 |
| Propylene yield | 29.6 |
Example 9
The remaining results are shown in Table 12, except that the palladium loading is 1% and the activity evaluation is conducted in accordance with example 6.
Table 12, example 9 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 49 |
| Propylene selectivity | 62 |
| Propylene yield | 30.4 |
Example 10
The remaining results are shown in Table 13, except that the palladium loading is 3% and the activity evaluation is performed in accordance with example 6.
TABLE 13 catalytic Activity of example 10
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 49 |
| Propylene selectivity | 61 |
| Propylene yield | 28.9 |
Example 11
The remaining results are shown in Table 14, except that the palladium loading is 5% in accordance with example 6.
TABLE 14 example 11 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 48 |
| Propylene selectivity | 62 |
| Propylene yield | 29.8 |
Example 12
The remaining results are shown in Table 15, except that the palladium loading was 8% in accordance with example 6.
Table 15, example 12 catalytic activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 47 |
| Propylene selectivity | 62 |
| Propylene yield | 29.1 |
Comparative example 4
The preparation process of the catalyst M/3Pt-10In/Al 2O3 In this example is as follows:
(1) 3Pt-10In/Al 2O3 was prepared as described In example 1.
(2) 1G of palladium nitrate was dissolved in 25ml of water as a precursor of palladium as an auxiliary. 0.4g of 3Pt-10In/Al 2O3 is weighed, 2.4ml of palladium nitrate solution is added to ensure that the palladium loading amount is 10 percent, the catalyst is dried overnight at 80 ℃, and the catalyst containing auxiliary agent palladium is obtained after roasting for 3 hours at 225 ℃ In a muffle furnace, and the catalyst is recorded as 10Pd/3Pt-10In/Al 2O3.
The material catalytic propane oxidative dehydrogenation test was consistent with example 1 and the activity evaluation results are shown in table 16.
Table 16, comparative example 2 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 45 |
| Propylene selectivity | 56 |
| Propylene yield | 25.2 |
From examples 6 to 12 and comparative example 4, it can be seen that the mass% of palladium directly affects the catalytic activity of the catalyst when the auxiliary palladium is added, and that the mass% of palladium is preferably 0.03 to 8%, more preferably 0.1 to 8%, still more preferably 0.5 to 1%.
Example 13
The remainder was identical to example 10, except that 1ml of chloroauric acid solution (10.0 mg/ml) was added simultaneously with the palladium nitrate solution, and the gold loading was 1%, which was recorded as 1Au-3Pd/3Pt-10In/Al 2O3. The results of the activity evaluation are shown in Table 17.
TABLE 17 example 13 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 50 |
| Propylene selectivity | 55 |
| Propylene yield | 27.5 |
Example 14
The remaining points were the same as In example 10 except that 5ml of a silver nitrate solution (2.0 mg/ml) was added together with the palladium nitrate solution, the silver loading was 1%, and the activity evaluation results were shown In Table 18 as 1Ag-3Pd/3Pt-10In/Al 2O3.
TABLE 18 example 14 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 54 |
| Propylene selectivity | 52 |
| Propylene yield | 28.1 |
Example 15
The remaining portions were the same as In example 10 except that 1ml of a ruthenium chloride solution (10.0 mg/ml) was added together with the palladium nitrate solution, the loading amount of ruthenium was 1%, and it was recorded as 1Ru-3Pd/3Pt-10In/Al 2O3, and the activity evaluation results were shown In Table 19.
Table 19, example 15 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 59 |
| Propylene selectivity | 51 |
| Propylene yield | 30.1 |
Example 16
The remaining points were the same as In example 10 except that 10ml of a cobalt nitrate solution (3.0 mg/ml) was added together with the palladium nitrate solution, the cobalt loading was 3%, and the results of activity evaluation were shown In Table 20, as 3Co-3Pd/3Pt-10In/Al 2O3.
Table 20, example 16 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 50 |
| Propylene selectivity | 71 |
| Propylene yield | 35.5 |
Example 17
The remaining points were the same as In example 10 except that 10ml of cerium nitrate solution (3.0 mg/ml) was added together with the palladium nitrate solution, the cerium loading was 3%, and the results of activity evaluation were shown In Table 21, as 3Ce-3Pd/3Pt-10In/Al 2O3.
Table 21, example 17 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 50 |
| Propylene selectivity | 65 |
| Propylene yield | 32.5 |
Example 18
The remaining points were the same as In example 10 except that 3ml of a copper acetate solution (10.0 mg/ml) was added together with the palladium nitrate solution, the copper loading was 3%, and the results of activity evaluation were shown In Table 22, as 3Cu-3Pd/3Pt-10In/Al 2O3.
Table 22, example 18 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 52 |
| Propylene selectivity | 67 |
| Propylene yield | 34.8 |
Example 19
The remainder was identical to example 18, except that the palladium loading was 5%, the copper loading was 3%, and the activity evaluation results were table 23.
TABLE 23 catalytic Activity of example 19
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 54 |
| Propylene selectivity | 68 |
| Propylene yield | 36.7 |
Example 20
The remainder was identical to example 18, except that the palladium loading was 1%, the copper loading was 4%, and the activity evaluation results were table 24.
TABLE 24 example 20 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 50 |
| Propylene selectivity | 69 |
| Propylene yield | 34.5 |
Comparative example 5
The remainder was identical to example 18, except that the palladium loading was 0.1%, the copper loading was 5%, and the activity evaluation results were table 25.
Table 25, comparative example 5 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 49 |
| Propylene selectivity | 52 |
| Propylene yield | 25.5 |
As can be seen from examples 13-20 and comparative example 5, the addition of certain amounts of other adjuvants to 3Pd/3Pt-10In/Al 2O3 can increase its catalytic activity, such as Ru, co, ce, cu; taking copper as an example, when the copper loading in the catalyst is 3% -4%, the catalytic activity of the catalyst can be further improved. When the palladium loading was 0.1% and the copper loading was 5%, the catalytic activity was rather lowered as compared to the case where no copper was added.
Example 21
The preparation process of the catalyst M/3Pt-10In/Al 2O3 In this example is as follows:
(1) 3Pt-10In/Al 2O3 was prepared as described In example 1.
(2) 1G of cobalt nitrate was dissolved in 25ml of water as a precursor of co-cobalt. 1g of cerium nitrate was dissolved in 25ml of water as a precursor of cerium as an auxiliary. 0.4g of 3Pt-10In/Al 2O3 was weighed, 1.5ml of cobalt nitrate solution was added, and 0.28ml of cerium nitrate was added to make the cobalt loading 3% and the cerium loading 1%. Drying overnight at 80 ℃, and roasting for 3 hours at 225 ℃ In a muffle furnace to obtain the catalyst containing the auxiliary agent cobalt and cerium, namely 3Co-1Ce/3Pt-10In/Al 2O3.
The material catalytic propane oxidative dehydrogenation test was consistent with example 1 and the activity evaluation results are shown in table 26.
Table 26, example 21 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 52 |
| Propylene selectivity | 72 |
| Propylene yield | 37.4 |
Example 22
The rest was the same as in example 21 except that the cobalt-removing load was 5%, the cerium load was 3%, and the activity evaluation results were table 27.
TABLE 27 example 22 catalytic Activity
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Example 23
The rest was the same as in example 21 except that the cobalt-removing load was 8%, the cerium load was 5%, and the activity evaluation results were Table 28.
Table 28, example 23 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 51 |
| Propylene selectivity | 70 |
| Propylene yield | 35.7 |
Example 24
The rest was the same as in example 21 except that the cobalt-removing load was 8%, the cerium load was 7%, and the activity evaluation results were Table 29.
Table 29, example 24 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 51 |
| Propylene selectivity | 69 |
| Propylene yield | 35.2 |
Example 25
The rest was the same as in example 21 except that the cobalt-removing load was 8%, the cerium load was 8%, and the activity evaluation results were table 30.
Table 30, example 25 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 50 |
| Propylene selectivity | 68 |
| Propylene yield | 34.0 |
Example 26
The rest was the same as in example 21 except that the cobalt-removing load was 0, the cerium load was 3%, and the activity evaluation results were table 31.
TABLE 31 catalytic Activity of example 25
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 43 |
| Propylene selectivity | 69 |
| Propylene yield | 29.7 |
Example 27
The rest was the same as in example 21 except that the cobalt-removing load was 3%, the cerium load was 0, and the activity evaluation results were table 32.
Table 32, example 25 catalytic Activity
| Oxidative dehydrogenation performance of propane | ％ |
| Propane conversion | 41 |
| Propylene selectivity | 67 |
| Propylene yield | 27.5 |
It can be seen from examples 21-25 and examples 26-27 that the catalytic activity of the catalyst was greater when both platinum and cobalt were doped In 3Pt-10In/Al 2O3 than when either was doped alone or not.
Comparative example 6
The comparative example selects boron nitride to compare the performance of the catalyst in the propylene preparation reaction by oxidative dehydrogenation of propane, and comprises the following specific steps:
1) 300mg of commercial boron nitride (Alfa-Aesar Co.) was weighed, placed in a steel tube in a fixed bed reactor, and heated to 490 ℃ at 1 ℃/min under nitrogen atmosphere;
2) After the temperature in the step 1) is stable, introducing a reaction mixed gas, wherein the gas composition is that the volume ratio of propane is 4.3%, the volume ratio of oxygen is 2.15%, the rest is nitrogen, and the reaction time-space speed is 42L/g/h. The reaction temperature was 490℃and after ten minutes of stabilization, the product was detected using gas chromatography. The test results showed that the conversion of propane was 8.27% and the selectivity of propylene was 85.9%.
Stability examples
Example 28
The activity evaluation results are shown in Table 33 except that the reaction time was prolonged to 100 hours as in example 25.
TABLE 33 catalytic Activity of example 28
| Oxidative dehydrogenation performance of propane | Initial Activity% | Activity for 100 hours |
| Propane conversion | 50 | 49.8 |
| Propylene selectivity | 68 | 67.5 |
| Propylene yield | 34.0 | 33.6 |
As can be seen from Table 33, the catalyst of the present invention had excellent stability, and the propylene yield was not significantly reduced in the stability test for 100 hours.
The present application is described in detail above. It will be apparent to those skilled in the art that the present application can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the application and without undue experimentation. While the application has been described with respect to specific embodiments, it will be appreciated that the application may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. The application of some of the basic features may be done in accordance with the scope of the attached claims.
Claims (10)
1. The propane oxidative dehydrogenation catalyst is characterized by comprising an active component and a carrier, wherein the active component is loaded on the carrier, the active component is Pt monoatoms and In monoatoms, and the carrier is alumina;
The mass percentage of the active component Pt in the propane oxidative dehydrogenation catalyst is 0.1-10%;
the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 1-20%.
2. The process for preparing a propane oxidative dehydrogenation catalyst according to claim 1, comprising the steps of:
and adding a Pt precursor and an In precursor salt into the aqueous dispersion of alumina, and sequentially stirring, drying for the first time, roasting for the first time and reducing at different temperature sections to obtain the propane oxidative dehydrogenation catalyst.
3. The method for producing a propane oxidative dehydrogenation catalyst according to claim 2, characterized in that: the precursor of Pt is chloroplatinic acid;
the precursor of In is indium nitrate;
The concentration of the alumina in the aqueous dispersion of the alumina is 0.002-0.2 g/mL;
the temperature of the first drying is 50-80 ℃ and the time is 8-12 hours;
the temperature of the first roasting is 500-750 ℃ and the time is 1-3 hours;
The first firing is performed in an air atmosphere;
The reduction is carried out in 10% H 2 atmosphere at 150 deg.C, 200 deg.C, 250 deg.C and 490 deg.C for 0.5-2 hours.
4. The propane oxidative dehydrogenation catalyst is characterized by comprising an active component, a carrier and an auxiliary agent, wherein the active component and the auxiliary agent are loaded on the carrier, the active component is Pt monoatoms and In monoatoms, the auxiliary agent is one or more of gold, silver, palladium, ruthenium, cobalt, cerium and copper, and the carrier is alumina;
The mass percentage of the active component Pt in the propane oxidative dehydrogenation catalyst is 0.1-10%;
the mass percentage of the active component In the propane oxidative dehydrogenation catalyst is 1% -20%;
The mass percentage of each auxiliary agent in the propane oxidative dehydrogenation catalyst is 0.03-8%.
5. The oxidative dehydrogenation catalyst of propane according to claim 4, characterized in that: the auxiliary agent comprises a first auxiliary agent and a second auxiliary agent, and is any one of the following:
1) The first auxiliary agent is palladium, and the second auxiliary agent is any one of ruthenium, cobalt, cerium and copper;
2) The first auxiliary agent is cobalt, and the second auxiliary agent is cerium.
6. The process for preparing a propane oxidative dehydrogenation catalyst as set forth in claim 4 or 5, comprising the steps of:
(1) Adding a precursor of Pt and a precursor salt of In into a water dispersion liquid of alumina, and sequentially stirring, drying for the first time, roasting for the first time and reducing at different temperature sections;
(2) And immersing the product after the first roasting in an aqueous solution of a precursor of the auxiliary agent, and sequentially performing second drying and second roasting to obtain the propane oxidative dehydrogenation catalyst.
7. The process for producing a propane oxidative dehydrogenation catalyst according to claim 6, characterized in that: the precursor of Pt is chloroplatinic acid;
the precursor of In is indium nitrate;
The concentration of the alumina in the aqueous dispersion of the alumina is 0.002-0.2 g/mL;
the temperature of the first drying is 50-80 ℃ and the time is 8-12 hours;
the temperature of the first roasting is 500-750 ℃ and the time is 1-3 hours;
The first firing is performed in an air atmosphere;
The reduction at different temperature sections is carried out in 10% H 2 atmosphere, and the reduction is carried out at 150 ℃,200 ℃, 250 ℃ and 490 ℃ respectively for 0.5 to 2 hours in sequence;
The precursor of the auxiliary agent is chloride, nitrate, sulfate or acetate of the auxiliary agent;
the concentration of the precursor of the auxiliary agent in the aqueous solution of the precursor of the auxiliary agent is 0.02-0.04 g/ml;
The temperature of the secondary drying is 50-80 ℃ and the time is 8-12 hours;
The temperature of the second roasting is 150-450 ℃ and the time is 2-4 hours;
the second firing is performed in an air atmosphere.
8. A method for preparing propylene by catalytic oxidative dehydrogenation of propane comprises the following steps:
Oxidative dehydrogenation of propane in the presence of oxygen and a diluent gas under the catalytic action of the oxidative dehydrogenation catalyst of propane according to any one of claims 1 and 4-5 to obtain propylene.
9. The method according to claim 8, wherein: the propane oxidative dehydrogenation catalyst is heated to the oxidative dehydrogenation temperature in a reducing atmosphere;
the reducing atmosphere consists of 1-10% of reducing gas by volume percentage and balance gas by volume percentage;
The balance gas is nitrogen or argon;
The reducing gas is hydrogen or carbon monoxide.
10. The method according to claim 8 or 9, characterized in that: the volume percentage of the propane in the reaction gas consisting of the propane, the oxygen and the diluent gas is 3-20%;
the volume percentage of the oxygen in the reaction gas consisting of the propane, the oxygen and the diluent gas is 1.5-10%;
The dilution gas is nitrogen, helium or argon;
the temperature of the oxidative dehydrogenation is 400-600 ℃;
the reaction hourly space velocity of the propane oxidative dehydrogenation catalyst is from 42 to 60L/g/h, based on the reaction gas per gram of catalyst passed per unit time.
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