CN114054021B - Application of Cu catalyst in alkane dehydrogenation reaction - Google Patents

Application of Cu catalyst in alkane dehydrogenation reaction Download PDF

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CN114054021B
CN114054021B CN202010757292.9A CN202010757292A CN114054021B CN 114054021 B CN114054021 B CN 114054021B CN 202010757292 A CN202010757292 A CN 202010757292A CN 114054021 B CN114054021 B CN 114054021B
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propane
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CN114054021A (en
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刘晓艳
康磊磊
王爱琴
张涛
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Dalian Institute of Chemical Physics of CAS
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J27/24—Nitrogen compounds
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
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Abstract

The present invention relates to TiO (titanium dioxide) 2 A preparation method of a carrier-supported copper catalyst and application of the carrier-supported copper catalyst in photo-thermal synergistic catalysis of propane dehydrogenation. The catalyst can realize propane dehydrogenation under the low-temperature condition through photo-thermal synergistic catalysis to prepare propylene and combine acetone. Wherein Cu is the active center of the catalytic reaction; light-absorbing semiconductor TiO 2 Electrons can be transferred to Cu to initiate the reaction; moisture and carbon dioxide may act as oxidation aids for the reaction. The preparation method of the catalyst is simple and mild, and the obtained catalyst has excellent performance in producing propylene and acetone by low-temperature photo-thermal synergy.

Description

Application of Cu catalyst in alkane dehydrogenation reaction
Technical Field
The present invention relates to TiO (titanium dioxide) 2 A preparation method of a supported Cu catalyst and photo-thermal synergistic catalysis application thereof. Cu/TiO obtained in the present invention 2 The catalyst can realize the dehydrogenation of propane in a lower temperature interval to prepare corresponding propane under the photo-thermal synergistic condition, and can co-produce acetone. Wherein Cu is the active center of the reaction; tiO (titanium dioxide) 2 The carrier absorbs light and then activates Cu by electron transfer. The catalyst has obvious advantages in the aspect of producing propylene by low-temperature dehydrogenation of propane, and the preparation method is simple and convenient for large-scale production.
Background
The low-carbon olefin is a very important chemical raw material, and the market demands at home and abroad are vigorous and the gap is increased year by year. Taking propylene as an example, it can be used for producing polypropylene, propylene oxide, acrylonitrile, butanol octanol, acrylic acid and the like. Downstream propylene-based products play an important role in the fields of medical, chemical, industrial manufacturing, etc. At present, most of propylene sources are catalytic cracking and steam cracking in petroleum refineries, and a small part of propylene sources are from direct dehydrogenation of coal or natural gas to prepare olefin by methanol and propane. Under the large background of large-scale development and utilization of shale gas and natural gas, propane is taken as an important byproduct, and the direct dehydrogenation technology of the propane is widely focused on propylene production by virtue of propane which can be used instead of crude oil, so that the technology has become a hot spot for development of propylene preparation industry.
The process for preparing propylene by alkane dehydrogenation can be divided into two types, namely anaerobic dehydrogenation and oxidative dehydrogenation. Since the advent of the direct dehydrogenation technology of propane, industrialization has been achieved through continuous technological process updating and perfecting. However, the catalysts used in the propane direct dehydrogenation technology are supported Pt or Cr 2 O 3 Catalyst, pt is expensive and Cr 2 O 3 Has strong carcinogenesis effect. In addition, the reaction temperature of the propane direct dehydrogenation process is above 500 ℃, sintering or carbon deposition of the catalyst is easy to be initiated, so that the activity of the catalyst is reduced, and the propane direct dehydrogenation technology needs to continuously regenerate the catalyst to maintain the performance of the catalyst. The oxidative dehydrogenation route of propane is a strongly exothermic process, without thermodynamic equilibrium limitation, theoretically lowHigh-efficiency conversion can be realized under the temperature condition. However, due to O 2 Propylene (C-H bond energy: 361 kJ/mol) is more readily deeply oxidized to low value CO than propane (C-H bond energy: 401 kJ/mol) x Increasing the selectivity and yield of propylene remains a significant challenge. This patent describes a method for preparing Cu catalyst for photosensitive semiconductor TiO 2 The carrier is Cu, which is an active center, can be used for preparing propylene by dehydrogenating propane at low temperature under the light-heat synergistic condition, and can be used for co-producing acetone.
Disclosure of Invention
The invention provides a preparation method of a Cu catalyst and a low-temperature photo-thermal synergistic catalytic application thereof. The catalyst can realize the efficient dehydrogenation of propane in a lower temperature range under the photo-thermal synergistic condition to prepare propylene, and solves the problems that the existing catalyst is inactive at low temperature and poor in olefin selectivity at high temperature.
In the Cu catalyst of the present invention, the Cu content is 0.05 to 20% by weight.
The preparation method of the Cu catalyst is realized by the following steps:
adding TiO with the required proportion into Cu precursor solution with the concentration of 10-400 mg/mL 2 The powder is continuously stirred at 25-60 ℃ until the liquid is evaporated to dryness, and then is dried in an oven at 60-120 ℃ for 4-12 h. And grinding the solid, and roasting at 250-500 ℃ for 1-6 hours, so as to obtain the Cu catalyst with photo-thermal synergistic catalytic activity.
The catalyst has mild preparation condition and simple process, is suitable for large-scale production, can convert propane into propylene under the condition of photo-thermal synergistic catalysis, and can co-produce acetone.
Drawings
FIG. 1 Cu/TiO loadings on a per gram catalyst basis 2 Propylene yield of the catalyst;
FIG. 2 different loadings of Cu/TiO in terms of Cu per gram 2 Propylene yield of the catalyst;
FIG. 3 is a mass spectrum of the liquid phase product;
FIG. 4.0.1% Cu/TiO 2 Scanning transmission electron microscopy pictures after roasting the catalyst;
FIG. 5.0.1% Cu/TiO 2 Scanning transmission electron microscopy pictures after the catalyst is reduced and passivated;
FIG. 6.0.1% Cu/TiO 2 Scanning transmission electron microscopy pictures after the catalyst reaction;
FIG. 7.80℃propylene yields for different supports carrying 0.1% Cu catalyst;
FIG. 8.80℃TiO 2 Propylene yields with different metal catalysts supported;
FIG. 9.80℃shows propylene yields under different reaction conditions;
FIG. 10.80℃the effect of moisture and carbon dioxide on propylene yield;
Detailed Description
The technical scheme of the invention is not limited to the following specific embodiments.
Example 1. To 0.19mL of copper nitrate trihydrate solution at a concentration of 20mg/mL, 1.71mL of deionized water was added and thoroughly mixed; adding 1g of P25 powder, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, the mixture was calcined in air at 400℃for 2 hours to give a Cu/P25 catalyst having a theoretical Cu content of 0.1% (referred to as 0.1% Cu/TiO) 2 )。
Example 2 to 0.95mL of copper nitrate trihydrate solution at a concentration of 20mg/mL was added 0.95mL of deionized water and thoroughly mixed; adding 1g of P25 powder, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, the mixture was calcined in air at 400℃for 2 hours to give a Cu/P25 catalyst having a theoretical Cu content of 0.5% (referred to as 0.5% Cu/TiO) 2 )。
Example 3 to 1.9mL of copper nitrate trihydrate solution at a concentration of 20mg/mL, 0mL of deionized water was added and thoroughly mixed; adding 1g of P25 powder, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; grinding, roasting in 400 ℃ air for 2 hours to obtain the Cu/P25 catalyst with the theoretical content of Cu of 1 percent(noted as 1% Cu/TiO) 2 )。
Example 4. To 1.9mL of copper nitrate trihydrate solution at a concentration of 40mg/mL, 0mL of deionized water was added and thoroughly mixed; adding 1g of P25 powder, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, roasting in air at 400 ℃ for 2 hours, and obtaining a Cu/P25 catalyst (named as 2% Cu/TiO) with the theoretical content of Cu of 2% 2 )。
Example 5 to 1.9mL of copper nitrate trihydrate solution at a concentration of 100mg/mL, 0mL of deionized water was added and thoroughly mixed; adding 1g of P25 powder, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, roasting in air at 400 ℃ for 2 hours, and obtaining a Cu/P25 catalyst (marked as 5% Cu/TiO) with the theoretical content of Cu of 5% 2 )。
Example 6. To 1.9mL of copper nitrate trihydrate solution at a concentration of 200mg/mL, 0mL of deionized water was added and thoroughly mixed; adding 1g of P25 powder, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, the mixture was calcined in air at 400℃for 2 hours to give a Cu/P25 catalyst having a theoretical Cu content of 10% (referred to as 10% Cu/TiO) 2 )。
Example 7. 1.71mL of deionized water was added to 0.19mL of a copper nitrate trihydrate solution at a concentration of 20mg/mL and thoroughly mixed; 1g CeO was added 2 Continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, roasting in air at 400 ℃ for 2 hours, and obtaining a Cu catalyst (named Cu/CeO) with the theoretical content of Cu of 0.1 percent after grinding 2 )。
Example 8 to 0.19mL of copper nitrate trihydrate solution at a concentration of 20mg/mL was added 1.71mL of deionized water and thoroughly mixed; 1g of WO is added 3 Continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, 400 DEG CRoasting in air for 2h, grinding to obtain Cu catalyst with theoretical Cu content of 0.1% (Cu/WO) 3 )。
EXAMPLE 9.2g of P25 were reduced in hydrogen at 600℃for 2h to give hydrogenated TiO 2 The powder is ready for use. 1.71mL of deionized water was added to 0.19mL of copper nitrate trihydrate solution at a concentration of 20mg/mL and thoroughly mixed; 1g of hydrogenated TiO is added 2 Continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, roasting in air at 400 ℃ for 2 hours, and obtaining a Cu catalyst (called Cu/TiO) with the theoretical content of Cu of 0.1 percent after grinding 2 (H))。
Example 10 to 0.19mL of copper nitrate trihydrate solution at a concentration of 20mg/mL, 1.71mL of deionized water was added and thoroughly mixed; 1g of BaTiO is added 3 Continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, the mixture was calcined in air at 400℃for 2 hours to give a Cu catalyst (referred to as Cu/BaTiO) having a theoretical Cu content of 0.1% 3 )。
Example 11 to 0.19mL of copper nitrate trihydrate solution at a concentration of 20mg/mL, 1.71mL of deionized water was added and thoroughly mixed; add 1g C 3 N 4 Continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, the mixture was calcined in air at 400℃for 2 hours to give a Cu catalyst having a theoretical Cu content of 0.1% (referred to as Cu/C) 3 N 4 )。
Example 12. To 0.43mL of 10mg/mL ferric nitrate solution, 1.47mL of deionized water was added and thoroughly mixed; adding 1g of P25, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, the mixture was calcined in air at 400℃for 2 hours to give a Fe catalyst (referred to as Fe/TiO) having a theoretical Fe content of 0.1% 2 )。
Example 13 to 0.5mL of a 10mg/mL solution of cobalt nitrate hexahydrate was added 1.4mL deionized water and thoroughly mixed;adding 1g of P25, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, roasting in air at 400 ℃ for 2 hours, and obtaining a Co catalyst (called Co/TiO) with the theoretical content of Co of 0.1 percent after grinding 2 )。
Example 14. 1.4mL of deionized water was added to 0.5mL of nickel nitrate hexahydrate solution at a concentration of 10mg/mL and thoroughly mixed; adding 1g of P25, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, the mixture was calcined in air at 400℃for 2 hours to give a Ni catalyst (referred to as Ni/TiO) having a Ni content of 0.1% by theory 2 )。
Example 15. 1.45mL deionized water was added to 0.45mL of a 10mg/mL zinc nitrate hexahydrate solution and thoroughly mixed; adding 1g of P25, and continuously stirring until the mixture is uniform; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; grinding, roasting in 400 deg.c air for 2 hr to obtain Zn catalyst with Zn content of 0.1 wt% (named Zn/TiO) 2 )。
Example 16. 1g of P25 powder was added to 1.9mL of deionized water and stirred continuously until homogeneous; transferring the mixture to a 45 ℃ oven, continuously heating until the liquid is completely evaporated to dryness, heating to 60 ℃, and continuously drying for 12 hours; after grinding, the mixture was calcined in air at 400℃for 2 hours to give treated P25 (designated as TiO 2 )。
Example 17 evaluation of different loadings of Cu/TiO from examples 1, 2, 3, 4, 5, 6 in the Activity test of the catalyst by photo-thermal co-catalytic propane dehydrogenation as a probe reaction 2 The activity of the catalysts was compared on the basis of propylene yield. The test conditions were: the diameter of a photosensitive window of the top-illuminated sleeve photo-thermal synergistic reactor (patent number: 201911170165.2) is 30mm, 80mg of catalyst is uniformly spread on an inner tube quartz sand plate (the estimated catalyst bed thickness is about 30 mu m) so as to ensure that the surface of each catalyst particle is irradiated by a xenon lamp light source; xenon lamp energy density of 500mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The composition (volume ratio) of the raw material gas is 23%C 3 H 8 、23％CO 2 、4％H 2 O, 50% He, raw material gas space velocity of 7500 mL.g -1 ·h -1 . Catalyst was tested with 10% H 2 He (v/v) was reduced in situ at 300℃for 2 hours. The reaction gas phase product was analyzed on-line by gas chromatography (agilent, 7890B) equipped with a 5A and Porapak Q packed column and TCD; the liquid phase product was analyzed by gas chromatography-mass spectrometry (Agilent 7890B-5977A GC/MSD).
Cu/TiO with different loading amounts in the range of 60-160 DEG C 2 The propylene yield of the catalyst tends to increase and then decrease. As shown in FIG. 1, the propylene yield per gram of catalyst was 0.1% Cu/TiO 2 The activity of the catalyst at low temperature (60-80 ℃) is higher than 0.5%, 1% and 10% Cu/TiO 2 Catalyst, and less than 2% and 5% Cu/TiO 2 A catalyst; overall, in the range of 0.1-5% Cu loading, cu/TiO 2 The activity of the catalyst increases with increasing loading. However, when the Cu loading was increased to 10%, cu/TiO was obtained 2 The activity of the catalyst is significantly reduced. When the yield of propylene is calculated by per gram of Cu, and the Cu loading is reduced to 0.1%, the activity of the catalyst is greatly improved; whereas the activity of the catalyst decreased significantly with increasing Cu loading (fig. 2). The above results indicate that Cu is the active site for the propane dehydrogenation to propylene: when the Cu loading is reduced to 0.1%, the utilization rate of Cu is highest; as Cu loading increases, cu utilization decreases substantially. Thus, 0.1% Cu/TiO 2 The catalyst has certain advantages in the low temperature (60-80 ℃) both in the overall activity of the catalyst and the utilization rate of Cu. Furthermore, for different loadings of Cu/TiO 2 The liquid phase product of the catalyst is detected by a gas chromatograph-mass spectrometer, and the mass spectrum result is matched with acetone (figure 3) through a database, and the yield is 5-50 mu mol g Cu -1 h -1 。
FIGS. 4, 5 and 6 are each 0.1% Cu/TiO 2 Scanning transmission electron micrograph after roasting, in situ reduction and passivation and reaction show no obvious Cu particles, indicating Cu is uniformly dispersed in TiO 2 No TiO is caused on the surface in-situ reduction and reaction process 2 Aggregation of Cu on the surface of the carrier.
Example 18 the activity of the different supported Cu catalysts obtained in examples 7, 8, 9, 10, 11 was evaluated under the same test conditions as in example 17 and compared with 0.1% Cu/TiO at 80℃in example 17 2 Comparison of the activity of the catalysts.
As can be seen from FIG. 7, the yield of propylene per gram of Cu at 80℃is compared with TiO 2 The highest Cu catalyst activity as a carrier reaches 50.6 mu mol g Cu -1 s -1 The method comprises the steps of carrying out a first treatment on the surface of the With CeO 2 And WO 3 The Cu catalyst as a carrier was slightly active, 0.6 and 0.3. Mu. Mol g, respectively Cu -1 s -1 The method comprises the steps of carrying out a first treatment on the surface of the By hydrogenation of TiO 2 、BaTiO 3 And C 3 N 4 The Cu catalyst as a carrier is not active at all. Wherein WO 3 Hydrogenated TiO 2 And C 3 N 4 The light absorption performance of (C) is better than that of TiO 2 But the catalytic activity is obviously lower than that of Cu/TiO 2 A catalyst. Therefore, when the Cu catalyst is used for preparing propylene by photo-thermal synergistic catalysis of propane dehydrogenation, the Cu catalyst is not only related to the light absorption range of the carrier, but also depends on the acid-base property, defect position and other chemical properties of the carrier.
Example 19 under the same test conditions as in example 17, the TiO obtained in examples 12, 13, 14, 15 was evaluated 2 Catalytic Activity of the supported different Metal catalysts and was equivalent to 0.1% Cu/TiO at 80℃in example 17 2 Comparison of the activity of the catalysts. The yield of propylene per gram of metal is used as a comparison standard, based on Cu/TiO 2 The propylene yield of (2) was 50.6. Mu. Mol g Cu -1 s -1 ；Fe/TiO 2 And Ni/TiO 2 The catalyst was slightly active, 2.5 and 4.1. Mu. Mol g, respectively M -1 s -1 The method comprises the steps of carrying out a first treatment on the surface of the And Co/TiO 2 And Zn/TiO 2 The catalyst is completely inactive. Thus, cu is the most active of the above metals in photo-thermal co-catalytic propane dehydrogenation reactions (see fig. 8).
Comparative example 1 evaluation of 0.1% Cu/TiO from example 1 when no light is applied and the other conditions are the same as the test conditions of example 17 2 Thermal catalytic activity of the catalyst. The results show that when heated only 0.1% Cu/TiO 2 The catalyst is totally inactive. Thus, the reaction process for producing propylene by dehydrogenation of propane requires light to activate the reaction (see fig. 9).
Comparative example 2. The TiO obtained in example 16 was evaluated under the same test conditions as in example 17 2 And with 0.1% Cu/TiO in example 17 at 80 DEG C 2 Propylene yield of the catalyst was compared. Cu/TiO under photo-thermal synergistic catalysis condition at 80 DEG C 2 The activity of the catalyst is the highest; under the light and heat synergistic condition, tiO 2 Nor is it active at all. The results indicate that Cu is the active center of the reaction (see fig. 9).
Comparative example 3 raw material gas ratio was adjusted to 23% C 3 H 8 、4％H 2 O, 73% He, other conditions were the same as those tested in example 17, for 0.1% Cu/TiO obtained in example 1 2 The catalyst was tested for activity to investigate the carbon dioxide versus Cu/TiO 2 Influence of the catalytic properties of the catalyst. As in example 17, 0.1% Cu/TiO 2 Propylene yield of the catalyst (50.6. Mu. Mol g Cu -1 s -1 ) In contrast, the propylene yield without carbon dioxide was reduced to 28.5. Mu. Mol g Cu -1 s -1 Indicating that the participation of carbon dioxide helps to increase the yield of propylene (see figure 10).
Comparative example 4 raw material gas ratio was 23% C 3 H 8 、23％CO 2 54% He, other conditions were the same as those tested in example 17, for example 1, 0.1% Cu/TiO 2 The catalyst was tested for activity to investigate the moisture vs. Cu/TiO 2 Influence of the catalytic properties of the catalyst. As in example 17, 0.1% Cu/TiO 2 Propylene yield of the catalyst (50.6. Mu. Mol g Cu -1 s -1 ) And propylene yield (28.5. Mu. Mol g) in comparative example 3 Cu -1 s -1 ) In contrast, the propylene yield without the participation of moisture was reduced to 3.3. Mu. Mol g Cu -1 s -1 . Therefore, the catalytic activity is highest when moisture and carbon dioxide are present at the same time; the activity was reduced without the addition of carbon dioxide or moisture, wherein the moisture had a greater effect on the catalytic activity (see FIG. 10).
As can be seen from the above examples and comparative examples, cu/TiO 2 The catalyst can pass through TiO under the photo-thermal synergistic condition 2 The photo-generated electrons generated on the surface are transferred to the surface of the active center Cu of the catalyst, so that propane is activated to prepare propylene, the reaction is milder than thermal catalysis, and propylene can be co-produced. Cu/TiO with low loading 2 The catalyst has higher activity, and proper amounts of water vapor and carbon dioxide can effectively improve the catalytic reaction activity of the reaction. The performance of the catalyst under the photo-thermal synergistic condition is obviously superior to that of the traditional thermal catalysis, and the preparation method is simple and mild, thereby providing a new way for developing low-temperature catalysis of low-carbon alkane dehydrogenation to prepare olefin.

Claims (10)

1. An application of a Cu catalyst in alkane dehydrogenation reaction, which is characterized in that:
the Cu catalyst is a supported catalyst with metal Cu as an active component, and the carrier is TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The Cu content in the catalyst is 0.05-20wt%; the reaction temperature is 40-180 ℃, and alkane dehydrogenation reaction is carried out under the illumination condition; the alkane dehydrogenation reaction is photo-thermal synergistic catalytic propane dehydrogenation reaction; in the photo-thermal synergistic catalytic propane dehydrogenation reaction, water vapor or water vapor and carbon dioxide are used as reaction auxiliary agents to improve the yield of olefin; in the reaction raw material gas, the volume concentration of water gas is 1% -10%, the volume concentration of carbon dioxide is 0% -50%, the balance is propane or propane and inert atmosphere gas, and the volume concentration of propane in the raw material gas is more than 5%; the space velocity of the raw material gas is 5000-30000 mL.g -1 ·h -1 ；
The preparation process of the Cu catalyst adopts an impregnation method to prepare the Cu catalyst in TiO 2 The carrier carries Cu:
adding TiO with a required proportion into Cu precursor solution with the concentration of 10-400 mg/mL 2 Continuously stirring the carrier at 25-60 ℃ until the liquid is evaporated to dryness, and drying the carrier in an oven at 60-120 ℃ for 4-12 hours;
grinding the solid, roasting at 250-500 ℃ for 1-6 hours, and grinding to obtain the Cu catalyst;
the supported metal Cu is the active center of the catalyst; tiO (titanium dioxide) 2 Absorbing ultraviolet light to generate electricityA daughter, and transfer to the Cu surface, thereby causing propane dehydrogenation to occur at low temperature conditions;
in the reaction products, the main product is co-produced with acetone except olefin.
2. The use according to claim 1, characterized in that:
the Cu content in the catalyst is 0.05-10 wt%, and the reaction temperature is 60-160 ℃.
3. The use according to claim 1, characterized in that:
the Cu content in the catalyst is 0.05-0.2 wt%, and the reaction temperature is 60-100 ℃;
the Cu content in the catalyst is more than 0.2% and less than or equal to 1% by weight, and the reaction temperature is 80-140 ℃;
the Cu content in the catalyst is more than 1% and less than or equal to 5% by weight, and the reaction temperature is 60-160 ℃;
the Cu content in the catalyst is more than 5% and less than or equal to 20% by weight, and the reaction temperature is 80-120 ℃.
4. The use according to claim 1, characterized in that:
the power density of light required by the photo-thermal synergistic reaction is 5-2000 mW/cm 2 The reaction rate increases with increasing optical power density.
5. The use according to claim 4, characterized in that:
the power density of light required by the photo-thermal synergistic reaction is 300-2000 mW/cm 2 。
6. The use according to claim 1, characterized in that:
in the reaction raw material gas, the volume concentration of water gas is 2-6%, and the volume concentration of carbon dioxide is 2-20%.
7. The use according to claim 1, characterized in that:
inert atmosphere gas is He, ar and N 2 One or more than two of them.
8. The use according to claim 1, characterized in that:
TiO 2 is anatase TiO 2 Crystal red stone TiO 2 One or more of P25.
9. The use according to claim 8, characterized in that:
the TiO 2 Is commercial TiO without any treatment 2 。
10. The use according to claim 1, characterized in that:
the Cu precursor solution is one or more than two of copper nitrate, copper acetylacetonate, copper chloride or copper sulfate.
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