CN113000044B - Carbon dioxide oxidation ethane dehydrogenation catalyst and preparation method thereof - Google Patents
Carbon dioxide oxidation ethane dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN113000044B CN113000044B CN202110276410.9A CN202110276410A CN113000044B CN 113000044 B CN113000044 B CN 113000044B CN 202110276410 A CN202110276410 A CN 202110276410A CN 113000044 B CN113000044 B CN 113000044B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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Abstract
The invention relates to a dehydrogenation catalyst for oxidizing ethane by carbon dioxide and a preparation method thereof, belonging to the technical field of catalysts. The invention aims to provide a preparation method of a dehydrogenation catalyst for oxidizing ethane by carbon dioxide. The method comprises the following steps: the cerium salt, the ethyl orthosilicate and the solvent are mixed evenly, ammonia water is dripped to the mixture under stirring until the pH value is 8.5 to 9.5, the mixture is continuously stirred for 0.5 to 2 hours, then the mixture is aged for 20 to 30 hours, solid-liquid separation is carried out, the solid is dried and then is roasted in oxygen-containing atmosphere, and the catalyst for dehydrogenation of carbon dioxide oxidized ethane is obtained. The method is simple and low in cost, and the catalyst obtained by the method has good catalytic activity and selectivity, and can be suitable for CO 2 In the ODHE reaction, the selectivity of ethylene is improved while the time required for the reaction to reach stable performance is reduced.
Description
Technical Field
The invention relates to a dehydrogenation catalyst for oxidizing ethane by carbon dioxide and a preparation method thereof, belonging to the technical field of catalysts.
Background
Oxidative dehydrogenation of ethane (CO) by carbon dioxide 2 -ODHE) is a new process for the production of ethylene starting from ethane, using the greenhouse gas CO 2 As an oxidant with milder activity, the catalyst can improve the selectivity of ethylene by effectively inhibiting the deep oxidation of reaction intermediate products, and simultaneously, CO is used 2 As a carbon source, the carbon source can also relieve the adverse effect of greenhouse gases on the environment. However, limited by current catalyst productivity, CO 2 The large-scale industrial production of ODHE is not realized.
At present, for CO 2 The most commonly used metal oxide catalysts for the-ODHE reaction are Cr, V, ga, in and Co, respectively. The Cr-based catalyst has multiple valence ions of Cr, and oxidation-reduction circulation is easily formed between high valence ions and low valence ions to CO 2 The ODHE has very good catalytic performance and is the most studied transition metal oxide catalyst at present. Cr-based catalysts tend to exhibit higher ethane conversion in a short time, but have a shorter lifetime due to their CO-to-CO ratio 2 The conversion rate is low, and the catalyst is easy to deposit carbon. The Cr oxide is loaded on SiO 2 When the catalyst is carried on carriers such as MCM-41, H-ZSM-5 and the like, the activity of the catalyst is greatly improved, and although Cr can be well dispersed in mesopores and can expose more active sites, more Cr exists in the form of low-activity polychromate. Increase Cr 6+ /Cr 3+ The ratio of (3) is a main method for improving the activity of the Cr-based catalyst, li and the like realize the regulation and control of the ratio of Cr < 6+ >/Cr < 3+ > of the Cr-based catalyst by introducing different additives, and further improve the activity of the catalyst. Despite these advances, chromium catalysts have short lifetimes, and Cr 3+ The high toxicity of (a) has to be careful in preparing, using and disposing of the material, and thus its wide application is limited. Because V ions can be switched between trivalent, tetravalent, and pentavalent, there has been much research on V-based catalysts. Research on V-based catalysts has focused more on the support on which they are supported, since the activity of vanadium oxides, like chromium, depends on the influence of the support on reducibility, acidity and basicity and dispersibility. V-based catalysts hold great promise for Oxidative Dehydrogenation (ODH) reactions, but it remains a challenge to control the acidic sites that promote olefin cleavage, while there is some information about V 2 O 5 Dust health problems. Ga-based catalyst has good CO adsorption and activation 2 Ability to be applied to CO 2 -ODH. Unloaded Ga 2 O 3 Has better olefin selectivity, but the catalyst is quickly deactivated because of serious carbon deposition. And Ga after loading 2 O 3 Can make alkane and CO 2 Competitive adsorption occurs, resulting in lower conversion of alkanes.
From this, the mainstream catalysts studied in many cases today have the following problems: (1) the catalyst is affected by carbon deposition and is inactivated quickly. (2) Cr and V metals are toxic and not suitable for industrial application. (3) Partial catalyst activation of CO 2 The capacity is not strong, and the oxidation-reduction cycle is slowed down.
Cerium (Ce) is one of the most abundant and cheapest rare earth elements, and has good anti-carbon deposition capability because of its own good oxygen storage and release properties, which makes it have industrial application prospects.
Zhang Xiu Ling in "load type CeO 2 CO on catalyst 2 Research on reaction for preparing ethylene from ethane oxide in Yi Wen (Zhang Xiu Ling et al, load type CeO) 2 CO on catalyst 2 Study of reaction for preparing ethylene from Oxirane [ J]University of grand junior, 2006 (12): 25-34) and adopting an impregnation method to prepare the supported CeO 2 Catalysts and investigation thereof in CO 2 The catalytic performance of the reaction for preparing ethylene by oxidizing ethane is found to be CeO 2 /γ-Al 3 O 2 Catalyst pair CO 2 The reaction for preparing ethylene by oxidizing ethane has better catalytic activity, but only CeO is used 2 As an active center for catalyzing the reaction, both selectivity and stability are required to be further improved.
Disclosure of Invention
Aiming at the defects, the technical problem solved by the invention is to provide a preparation method of a dehydrogenation catalyst for oxidizing ethane by carbon dioxide, and the catalyst prepared by the method has good selectivity and stability.
The preparation method of the dehydrogenation catalyst for oxidizing ethane by carbon dioxide comprises the following steps:
evenly mixing cerium salt, tetraethoxysilane and solvent, dropwise adding ammonia water while stirring until the pH is 8.5-9.5, continuously stirring for 0.5-2 h, then aging for 20-30 h, carrying out solid-liquid separation, drying the solid, and roasting in an oxygen-containing atmosphere to obtain the carbon dioxide ethane oxide dehydrogenation catalyst.
In one embodiment of the invention, the cerium salt is Ce (NO) 3 ) 3 ·6H 2 O。
In one embodiment of the present invention, the molar ratio of silicon in the ethyl orthosilicate to cerium in the cerium salt is from 0.1 to 1.
In one embodiment, the solvent is ethanol.
In a preferred embodiment of the invention, ammonia is added to adjust the pH to 9.
In one embodiment of the invention, the temperature of the calcination is 550 to 700 ℃. In one embodiment of the invention, the temperature of calcination is 600 ℃.
In one embodiment of the present invention, the oxygen-containing atmosphere is an air atmosphere.
The invention also provides the carbon dioxide ethylene oxide dehydrogenation catalyst prepared by the preparation method of the carbon dioxide ethylene oxide dehydrogenation catalyst.
The invention relates to a dehydrogenation catalyst for oxidizing ethane by carbon dioxide, which uses CeO 2 As active sites for catalyzing this reaction, in CeO 2 The surface is covered with SiO with a certain thickness 2 The selectivity of the catalyst can be improved and the time required for the reaction to reach stable performance can be reduced.
Compared with the prior art, the method is simple and low in cost, and the catalyst obtained by the method has good catalytic activity and selectivity, and can be suitable for CO 2 In the ODHE reaction, the selectivity of ethylene is improved while the time required for the reaction to reach stable performance is reduced.
Drawings
FIG. 1 shows Si as a sample in example 1 0.1 -CeO 2 On He + 、Ne + LEIS plot after alternate sputtering.
FIG. 2 shows Si as a sample in example 2 0.3 -CeO 2 On He + 、Ne + LEIS plot after alternate sputtering.
FIG. 3 is a graph of the rate of consumption of reactants in a catalytic reaction experiment.
Figure 4 is a graph of the rate of ethylene production.
Detailed Description
The preparation method of the dehydrogenation catalyst for oxidizing ethane by carbon dioxide comprises the following steps:
evenly mixing cerium salt, tetraethoxysilane and solvent, dropwise adding ammonia water while stirring until the pH is 8.5-9.5, continuously stirring for 0.5-2 h, then aging for 20-30 h, carrying out solid-liquid separation, drying the solid, and roasting in an oxygen-containing atmosphere to obtain the carbon dioxide ethane oxide dehydrogenation catalyst.
The method adopts a coprecipitation method to prepare the carbon dioxide ethane oxide dehydrogenation catalyst. By adding in CeO 2 The surface is covered with SiO with a certain thickness 2 Can regulate and control the product distribution of the reactionHigh selectivity and stability of catalyst. In addition, the method has the advantages of wide raw material source, low price, simple preparation process and capability of reducing the cost of the catalyst.
Any cerium salt commonly used in the art may be suitable for use in the present invention, for example, cerium nitrate, cerium chloride, etc. In one embodiment of the invention, the cerium salt is Ce (NO) 3 ) 3 ·6H 2 O。
The use amount of the tetraethoxysilane can be adjusted to SiO 2 In one embodiment of the present invention, the molar ratio of silicon in the ethyl orthosilicate to cerium in the cerium salt is 0.1 to 1.
Solvents commonly used in the art to dissolve cerium salts and ethyl orthosilicate are suitable for use in the present invention. In one embodiment, the solvent is ethanol.
In a preferred embodiment of the invention, ammonia is added to adjust the pH to 9.
In one embodiment of the invention, the temperature of the calcination is 550 to 700 ℃. In one embodiment of the invention, the temperature of calcination is 600 ℃.
The calcination may be performed in an oxygen-containing atmosphere, and it is preferable for cost saving that the oxygen-containing atmosphere is an air atmosphere.
The invention also provides the carbon dioxide ethylene oxide dehydrogenation catalyst prepared by the preparation method of the carbon dioxide ethylene oxide dehydrogenation catalyst.
The invention relates to a dehydrogenation catalyst for oxidizing ethane by carbon dioxide, which uses CeO 2 As active centers for catalyzing the reaction, in CeO 2 The surface is covered with SiO with a certain thickness 2 The selectivity of the catalyst can be improved and the time required for the reaction to reach stable performance can be reduced.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Si was prepared as follows 0.1 -CeO 2 Catalyst:
at 60mlEthanol was added with 4.34g Ce (NO) 3 ) 3 ·6H 2 And O, adding a certain amount of Tetraethoxysilane (TEOS) according to the atomic ratio of Si to Ce of 0.1, stirring for 1 hour at room temperature to fully mix the materials, dropwise adding a certain amount of ammonia water to the solution until the pH of the solution is =9 within 30min at a constant speed, and then stirring the solution for 1 hour. The mixture was then aged at room temperature for 24h, subsequently filtered with suction and the solid obtained was dried at 100 ℃ for 12h. Finally, the catalyst is obtained by roasting in the air at 600 ℃. Sample is named Si 0.1 -CeO 2 。
Example 2
Si was prepared as follows 0.3 -CeO 2 Catalyst:
to 60ml of ethanol was added 4.34g of Ce (NO) 3 ) 3 ·6H 2 And O, adding a certain amount of Tetraethoxysilane (TEOS) according to the atomic ratio of Si to Ce of 0.3. The mixture was then aged at room temperature for 24h, subsequently filtered with suction and the solid obtained was dried at 100 ℃ for 12h. Finally, roasting the mixture in the air at the temperature of 600 ℃ to obtain the catalyst. Sample is named Si 0.3 -CeO 2 。
Example 3
Si was prepared as follows 0.6 -CeO 2 Catalyst:
to 60ml of ethanol was added 4.34g of Ce (NO) 3 ) 3 ·6H 2 And O, adding a certain amount of Tetraethoxysilane (TEOS) according to the atomic ratio of Si to Ce of 0.6, stirring for 1 hour at room temperature to fully mix the materials, dropwise adding a certain amount of ammonia water to the solution until the pH of the solution is =9 within 30min at a constant speed, and then stirring the solution for 1 hour. The mixture was then aged at room temperature for 24h, filtered with suction and the solid dried at 100 ℃ for 12h. Finally, the catalyst is obtained by roasting in the air at 600 ℃. Sample was named Si 0.6 -CeO 2 。
Example 4
Si was prepared as follows 1.0 -CeO 2 Catalyst:
to 60ml of ethanol was added 4.34g of Ce (NO) 3 ) 3 ·6H 2 And O, adding a certain amount of Tetraethoxysilane (TEOS) according to the atomic ratio of Si to Ce of 1. The mixture was then aged at room temperature for 24h, subsequently filtered with suction and the solid obtained was dried at 100 ℃ for 12h. Finally, the catalyst is obtained by roasting in the air at 600 ℃. Sample was named Si 1.0 -CeO 2 。
Comparative example 1
CeO was prepared by the following method 2 Catalyst:
to 60ml of ethanol was added 4.34g of Ce (NO) 3 ) 3 ·6H 2 And O, stirring for 1h at room temperature, uniformly dropping a certain amount of ammonia water into the solution within 30min until the pH of the solution is =9, and then stirring the solution for 1h. The mixture was then aged at room temperature for 24h, filtered with suction and the solid dried at 100 ℃ for 12h. Finally, roasting the mixture in the air at the temperature of 600 ℃ to obtain the catalyst. The sample was named CeO 2 。
To catalyst Si 0.1 -CeO 2 And Si 0.3 -CeO 2 Using He + And Ne + Alternately sputtering/analyzing the catalyst, performing Low Energy Ion Scattering (LEIS) test after each sputtering, arranging corresponding test spectral lines in sequence, and He + 、Ne + The LEIS diagram after the alternating sputtering is shown in fig. 1 and fig. 2. In the figure, kinetic Energy is expressed in eV. In Si 0.1 -CeO 2 In the catalyst, the signals of Si and Ce are weak in the initial stage of detection, and the signal of Ce is gradually increased with the increase of the sputtering times, while the signal of Si is weakened to disappear, which shows that in the sample, the trace amount of SiO is in the sample 2 Only in a few atomic layers on the outer surface of the catalyst and partially covered with CeO 2 . In Si 0.3 -CeO 2 In the catalyst, it can be seen that, from the beginning to the end of the experiment, the signal of Si is not changed, and the signal of Ce is also changed from weak to strong, which indicates that SiO 2 Uniformly present in several atomic layers on the surface, and with increasing depth, ceO 2 The content of (b) increases. It was found that the surface of the catalyst was SiO 2 OfSeparately covered, and this layer covered SiO 2 The thickness of the layer is positively correlated with the amount of Si source added during preparation, while SiO of suitable thickness 2 The selectivity of the layer to the catalyst is greatly improved.
The catalytic activity of the catalysts of examples 1 to 4 and comparative example 1 was measured. The Conversion (Conversion) and Conversion frequency (Turnover frequency, TOF) and the distribution of the products after the catalyst reaction are shown in Table 1. The reaction conditions are as follows: the catalyst dosage is 300mg, the atmospheric pressure and the temperature are 700 ℃, the reactant flow is 30mL/min, and the composition of reactants is as follows: c 2 H 6 :CO 2 :N 2 Ar = 20. The product distribution at 8h on stream is shown in Table 1.
The consumption rate of the reactants consumed in the catalytic reaction test is shown in fig. 3, the rate of ethylene production is shown in fig. 4, and in fig. 3 and 4, a: ceO (CeO) 2 ，b：Si 0.1 -CeO 2 。
TABLE 1
a TOF is based on total CeO 2 And (4) calculating.
It can be seen that the selectivity with respect to ethylene is greatly improved for the catalyst of the invention, in particular for Si, at the same TOF 0.6 -CeO 2 Compared with CeO 2 ，Si 0.6 -CeO 2 The selectivity of ethylene is improved by 57.7 percent on the original basis (24 percent).
In terms of stability, the catalyst of the invention only needs 20 hours to achieve stable performance, and 10 hours is reduced on the basis of the unmodified catalyst.
Claims (6)
1. The application of the dehydrogenation catalyst for oxidizing ethane by carbon dioxide is characterized in that the dehydrogenation catalyst is used for oxidizing ethane by carbon dioxide and is prepared by the following steps:
mixing cerium salt, ethyl orthosilicate and solvent, adding ammonia water dropwise under stirring till the pH is 8.5-9.5, and continuously stirring for 0.5EAging for 20-30 h, performing solid-liquid separation, drying the solid, and roasting in an oxygen-containing atmosphere to obtain a carbon dioxide ethane oxide dehydrogenation catalyst; the cerium salt is Ce (NO) 3 ) 3 ·6H 2 O；
The molar ratio of silicon in the ethyl orthosilicate to cerium in the cerium salt is 0.1-1.
2. Use of a catalyst for the dehydrogenation of carbon dioxide by oxidation of ethane according to claim 1, characterized in that: the solvent is ethanol.
3. Use of a catalyst for the dehydrogenation of carbon dioxide by oxidation of ethane according to claim 1, characterized in that: the pH was 9.
4. Use of a catalyst for the dehydrogenation of carbon dioxide by oxidation of ethane according to claim 1, characterized in that: the roasting temperature is 550-700 ℃.
5. Use of a catalyst for the dehydrogenation of carbon dioxide by oxidation of ethane according to claim 4, characterized in that: the calcination temperature was 600 ℃.
6. Use of a catalyst for the dehydrogenation of carbon dioxide by oxidation of ethane according to claim 1, characterized in that: the oxygen-containing atmosphere is air.
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| CA2752409C (en) * | 2011-09-19 | 2018-07-03 | Nova Chemicals Corporation | Membrane-supported catalysts and the process of oxidative dehydrogenation of ethane using the same |
| US9908101B2 (en) * | 2012-11-07 | 2018-03-06 | Council Of Scientific & Industrial Research | Catalyst for selective dehydrogenation / oxidative dehydrogenation reactions and process for the preparation thereof |
| CN109529857A (en) * | 2018-12-10 | 2019-03-29 | 江苏大学 | Ni@SiO2@CeO2The preparation method of nucleocapsid catalyst and its application in methane carbon dioxide reformation |
| CN110270321A (en) * | 2019-07-04 | 2019-09-24 | 南京大学 | The preparation method and its product of a kind of cerium Si composite oxide and application |
| CN113058586A (en) * | 2021-03-31 | 2021-07-02 | 四川大学 | Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof |
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