CN106582775B - Catalyst for preparing isobutene - Google Patents
Catalyst for preparing isobutene Download PDFInfo
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- CN106582775B CN106582775B CN201510672575.2A CN201510672575A CN106582775B CN 106582775 B CN106582775 B CN 106582775B CN 201510672575 A CN201510672575 A CN 201510672575A CN 106582775 B CN106582775 B CN 106582775B
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Abstract
The invention relates to a catalyst for preparing isobutene, a preparation method and application thereof, and mainly solves the problem of poor stability of the catalyst in the prior art. The catalyst for preparing isobutene by adopting isobutane dehydrogenation comprises a carrier, an active component and an auxiliary agent, and the technical scheme that the catalyst takes at least one of MCF and SAPO as the carrier, vanadium as the active component and one or more of Sb and rare earth metals as the auxiliary agent better solves the technical problem, and can be used for industrial production of isobutene by adopting isobutane dehydrogenation in a carbon dioxide atmosphere.
Description
Technical Field
The invention relates to a catalyst for preparing isobutene, a preparation method and application thereof.
Background
Isobutene is a very important chemical raw material, has very wide application in chemical production, and can be used for synthesizing methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), butyl rubber, ABS resin and the like. With the expansion of the production scale of isobutene downstream products, the demand of isobutene is continuously increased. The isobutene obtained by the traditional method cannot meet the market demand. In addition, the C4 resource in China is very rich, but compared with the European and American countries, the utilization rate of the C4 resource in China is lower and less than 40%, the C4 resource is only about half of that in the European and American countries, the utilization of olefin is mainly focused, most of alkane is used as fuel, and great resource waste is brought. The isobutene with high added value produced by dehydrogenating the isobutane with relatively low price can not only solve the shortage of the isobutene but also produce larger economic benefit.
The isobutene preparation by isobutane dehydrogenation mainly comprises three methods of catalytic dehydrogenation, oxygen oxidative dehydrogenation and carbon dioxide atmosphere dehydrogenation. Isobutane catalytic dehydrogenation is currently industrialized, but the reaction is limited by thermodynamic equilibrium and the energy consumption is relatively high. The oxidative dehydrogenation of isobutane by oxygen can bring about deep oxidation, uncontrolled distribution of products, low selectivity and the like. The method for preparing isobutene by dehydrogenating isobutane in the carbon dioxide atmosphere combines the advantages of catalytic dehydrogenation and oxygen oxidative dehydrogenation, and is a new method with potential competitive capacity. The carbon dioxide can generate a reverse water gas reaction with hydrogen generated by dehydrogenation, so that thermodynamic equilibrium limitation is broken, and the dehydrogenation reaction is moved to a product; or the carbon dioxide may be directly subjected to an oxidative dehydrogenation reaction with isobutane. Both mechanisms described above can increase the equilibrium conversion of isobutane. In addition, carbon dioxide is used as a main greenhouse gas, and is converted into carbon monoxide which is more active and easier to use industrially in the reaction process, so that the greenhouse emission is reduced, carbon resources are fully utilized, and the method has certain social value.
For example, the Ogonowski group VMgO catalyst has a conversion of 13% and a selectivity of 80% at a reaction temperature of 600 ℃ (catalysis communications, Vol. 11, 2009, pages 132-136). The Chinese patent CN102631914A prepared a vanadium pentoxide catalyst with mesoporous carbon as a carrier, and the conversion rate of isobutane was about 32% and the selectivity was about 91.4% at a reaction temperature of 610 ℃. Shimada et al used an activated carbon-supported iron oxide catalyst, where the isobutane conversion rate was about 23% and the selectivity was about 80% at a reaction temperature of 600 ℃, and the catalyst was deactivated quickly, and the isobutane conversion rate was reduced to 13% after 3 hours of reaction (Applied Catalysis A: General, vol. 168, 1998, pp. 243-250). Therefore, the activity of the catalyst is reduced along with the prolonging of the reaction time, and the improvement of the stability of the catalyst for preparing isobutene is one of the problems to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problem that the catalyst in the prior art is poor in stability, and provides a novel catalyst for preparing isobutene by dehydrogenating isobutane. The catalyst has the characteristic of good stability.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
The present invention is also directed to a catalyst, which can be used to solve the above problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for preparing isobutene comprises a carrier, an active component and an auxiliary agent, wherein the catalyst takes at least one of MCF and SAPO molecular sieves as the carrier, vanadium as the active component and one or more of Sb and rare earth metals as the auxiliary agent.
In the above technical solution, in terms of promoting the stability of the catalyst, the promoter has an interaction promoting effect between Sb and rare earth, for example, but not limited to, a promoting effect between Sb and Ce.
The rare earth metal is not particularly limited, such as but not limited to L a, Ce, Pr, Nd, Pm and the like among the light rare earth metal elements, but preferably the rare earth comprises Ce and Nd simultaneously, and the catalyst has better stability and has synergistic effect on the aspect of improving activity.
In the technical scheme, the mass percentage of vanadium calculated by V2O5 is preferably 0.6-29%, and more preferably 1-10%.
In the technical scheme, the mass percentage of Sb is preferably 0.1-5% calculated by Sb2O5
In the technical scheme, the mass percentage of the rare earth metal is preferably 0.3-5.0% calculated by the trivalent oxide of the rare earth.
To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the catalyst in the technical scheme of one of the technical problems comprises the following steps:
1) mixing the required amount of the carrier with the vanadium-containing solution and the auxiliary agent-containing solution in sequence, or mixing the required amount of the carrier with the vanadium-containing solution and the auxiliary agent-containing solution simultaneously;
2) and roasting to obtain the catalyst.
In the above technical solutions, the solution is preferably a solvent of water, and those skilled in the art know that, according to the properties of the vanadium-containing compound and the auxiliary-containing compound, the pH is adjusted by acid or alkali to dissolve the above compounds in water to form a solution.
The carrier may be mixed with the vanadium-containing solution and the solution containing the auxiliary in succession, without any restriction on the succession, or with a mixed solution containing both vanadium and auxiliary.
When the carrier is mixed with the vanadium-containing solution and the auxiliary agent-containing solution, the preparation method of the mixed solution can be, but is not limited to:
a. dissolving a required amount of vanadium compound in water, and dissolving a proper amount of 0.25 mol/L tartaric acid aqueous solution in a beaker to obtain a vanadium-containing aqueous solution;
b. b, adding required amount of antimony and rare earth compound into the vanadium-containing aqueous solution in the step a, and stirring and dissolving to obtain vanadium-containing and auxiliary agent-containing aqueous solution;
in the above technical scheme, the compound of vanadium is not particularly limited, such as but not limited to one of ammonium metavanadate, vanadyl sulfate and vanadyl oxalate, the compound of antimony is not particularly limited, such as but not limited to chloride salt, and the rare earth compound is also not particularly limited, such as but not limited to nitrate, chloride, etc.
In the technical scheme, the roasting temperature is preferably 550-850 ℃, and more preferably 600-700 ℃.
In the above technical scheme, the roasting time is preferably 2-10 hours, and more preferably 4-6 hours.
In the above-mentioned technical solutions, it is preferred to have a drying step between step 1) and step 2), as known to those skilled in the art.
In the technical scheme, the drying temperature is preferably 90-140 ℃.
In the above technical scheme, Ce in the final catalyst often exists in the form of CeO2, and other rare earth metals often exist in the form of trivalent oxides.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the catalyst is applied to the reaction of preparing isobutene by dehydrogenating isobutane in the carbon dioxide atmosphere.
In the technical scheme, the molar ratio of the carbon dioxide to the isobutane is preferably 1-10.
In the technical scheme, the reaction temperature is preferably 550-640 ℃.
In the technical scheme, the mass airspeed of the isobutane is 0.1-3 h < -1 >.
The isobutane conversion rate and the activity reduction rate were calculated according to the following formulas:
the greater the rate of activity decrease, the more unstable the catalyst and vice versa. When this value is negative, it indicates that the activity does not decrease or increase inversely, this is a more favorable result.
Under the experimental conditions of the invention, the catalyst for preparing isobutene can continuously run for 8h, has better stability and obtains better technical effect.
The invention is further illustrated by the following examples:
Detailed Description
[ example 1 ]
1. Catalyst preparation
Ammonium metavanadate corresponding to 8 g of V2O5, cerium nitrate corresponding to 2.5 g of CeO2, and antimony trichloride corresponding to 3.0 g of Sb2O5 were dissolved in 40 ml of a 0.25 mol/l aqueous solution of tartaric acid, mixed with 86.5 g of MCF carrier, left to stand at room temperature for 8 hours, dried at 120 ℃ for 24 hours, and finally calcined at 620 ℃ in a muffle furnace for 6 hours to obtain the desired catalyst, the composition of which is shown in table 1 for comparison.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 5.0, the reaction temperature is 575 ℃, the mass space velocity of the isobutane is 0.8 h < -1 >, and the reaction pressure is normal pressure.
For ease of comparison, the results of the catalyst activity evaluation are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
1. Catalyst preparation
Ammonium metavanadate corresponding to 8 g of V2O5 and cerium nitrate corresponding to 5.5 g of CeO2 were dissolved in 40 ml of a 0.25 mol/l aqueous solution of tartaric acid, mixed with 86.5 g of MCF carrier, left to stand at room temperature for 8 hours, dried at 120 ℃ for 24 hours, and finally calcined at 620 ℃ in a muffle furnace for 6 hours to obtain the desired catalyst, the composition of which is shown in table 1 for comparison.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 5.0, the reaction temperature is 575 ℃, the mass space velocity of the isobutane is 0.8 h < -1 >, and the reaction pressure is normal pressure.
For ease of comparison, the results of the catalyst activity evaluation are shown in Table 2.
[ COMPARATIVE EXAMPLE 2 ]
1. Catalyst preparation
Ammonium metavanadate corresponding to 8 g of V2O5 and antimony trichloride corresponding to 5.5 g of Sb2O5 were dissolved in 40 ml of a 0.25 mol/L aqueous solution of tartaric acid, mixed with 86.5 g of MCF carrier, allowed to stand at room temperature for 8 hours, dried at 120 ℃ for 24 hours, and finally calcined at 620 ℃ in a muffle furnace for 6 hours to obtain the desired catalyst, the composition of which is shown in Table 1 for comparison.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 5.0, the reaction temperature is 575 ℃, the mass space velocity of the isobutane is 0.8 h < -1 >, and the reaction pressure is normal pressure.
For ease of comparison, the results of the catalyst activity evaluation are shown in Table 2.
[ example 2 ]
1. Catalyst preparation
Ammonium metavanadate corresponding to 8 g of V2O5, neodymium nitrate corresponding to 2.5 g of Nd2O3, and antimony trichloride corresponding to 3.0 g of Sb2O5 were dissolved in 40 ml of a 0.25 mol/l aqueous solution of tartaric acid, mixed with 86.5 g of MCF carrier, left to stand at room temperature for 8 hours, dried at 120 ℃ for 24 hours, and finally calcined in a muffle furnace at 620 ℃ for 6 hours to obtain the desired catalyst, the composition of which is shown in table 1 for comparison.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 5.0, the reaction temperature is 575 ℃, the mass space velocity of the isobutane is 0.8 h < -1 >, and the reaction pressure is normal pressure.
For ease of comparison, the results of the catalyst activity evaluation are shown in Table 2.
[ example 3 ]
1. Catalyst preparation
Ammonium metavanadate corresponding to 8 g of V2O5, neodymium nitrate corresponding to 1.0 g of Nd2O3, cerium nitrate corresponding to 1.5 g of CeO2, and antimony trichloride corresponding to 3.0 g of Sb2O5 were dissolved in 40 ml of a 0.25 mol/l aqueous solution of tartaric acid, mixed with 86.5 g of MCF carrier, left to stand at room temperature for 8 hours, dried at 120 ℃ for 24 hours, and finally calcined in a muffle furnace at 620 ℃ for 6 hours to obtain the desired catalyst, and the composition of the catalyst is shown in table 1 for comparison.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 5.0, the reaction temperature is 575 ℃, the mass space velocity of the isobutane is 0.8 h < -1 >, and the reaction pressure is normal pressure.
For ease of comparison, the results of the catalyst activity evaluation are shown in Table 2.
[ example 4 ]
1. Catalyst preparation
Ammonium metavanadate corresponding to 8 g of V2O5 and praseodymium nitrate corresponding to 2.5 g of Pr2O3 were dissolved in 25 ml of a 0.25 mol/L aqueous oxalic acid solution, mixed with 90 g of the SBA-15 carrier, left to stand at room temperature for 4 hours, dried at 100 ℃ for 24 hours, and finally calcined at 600 ℃ for 4 hours to obtain the desired catalyst, the composition of which is shown in Table 1 for comparison.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 5.0, the reaction temperature is 590 ℃, the mass space velocity of the isobutane is 1.0 h < -1 >, and the reaction pressure is normal pressure.
For ease of comparison, the results of the catalyst activity evaluation are shown in Table 2.
[ example 5 ]
1. Catalyst preparation
Ammonium metavanadate corresponding to 8 g of V2O5, lanthanum nitrate corresponding to 2.5 g of L a 2O3 and antimony trichloride corresponding to 3.0 g of Sb2O5 were dissolved in 40 ml of 0.25 mol/l aqueous tartaric acid solution, mixed with 86.5 g of MCF carrier, left to stand at room temperature for 8 hours, then dried at 120 ℃ for 24 hours, and finally calcined in a muffle furnace at 620 ℃ for 6 hours to obtain the desired catalyst, the composition of which is shown in table 1 for comparison.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 5.0, the reaction temperature is 575 ℃, the mass space velocity of the isobutane is 0.8 h < -1 >, and the reaction pressure is normal pressure.
For ease of comparison, the results of the catalyst activity evaluation are shown in Table 2.
[ example 6 ]
1. Catalyst preparation
Ammonium metavanadate corresponding to 29 g of V2O5, cerium nitrate corresponding to 1.0 g of CeO2 and antimony trichloride corresponding to 0.5 g of Sb2O5 were dissolved in 45 ml of a 0.25 mol/L aqueous solution of tartaric acid, mixed with 69.5 g of MCF carrier, allowed to stand at room temperature for 8 hours, dried at 90 ℃ for 36 hours, and finally calcined at 800 ℃ in a muffle furnace for 2 hours to obtain the desired catalyst.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 2.0, the reaction temperature is 640 ℃, the mass space velocity of the isobutane is 1.0 hour-1, and the reaction pressure is normal pressure.
The reaction result is: when the reaction time is 30 minutes, the isobutane conversion rate is 30.6 percent; after a reaction time of 8 hours, the isobutane conversion was 29.1%.
[ example 7 ]
1. Catalyst preparation
Ammonium metavanadate equivalent to 1 g of V2O5, cerium nitrate equivalent to 5 g of CeO2 and antimony trichloride equivalent to 5 g of Sb2O5 are dissolved in 45 ml of 0.25 mol/L aqueous solution of tartaric acid, mixed with 89 g of SAPO-34 carrier, stood at room temperature for 8 hours, dried at 150 ℃ for 24 hours, and finally calcined in a muffle furnace at 580 ℃ for 10 hours to prepare the required catalyst.
2. Catalyst evaluation
The activity of the catalyst prepared by the method is evaluated in a fixed bed reactor, and the process is as follows:
the reactor had an inner diameter of 8 mm stainless steel tube and a length of 400 mm. The molar ratio of the carbon dioxide to the isobutane is 10.0, the reaction temperature is 550 ℃, the mass space velocity of the isobutane is 1.0 hour-1, and the reaction pressure is normal pressure.
The reaction result is: when the reaction time is 30 minutes, the isobutane conversion rate is 28.1 percent; after a reaction time of 8 hours, the isobutane conversion was 27.5%.
TABLE 1
| V2O5 | Sb2O5 | Nd2O3 | CeO2 | Pr2O3 | La2O3 | Carrier | |
| Example 1 | 8 | 3.0 | - | 2.5 | - | - | 86.5 |
| Comparative example 1 | 8 | - | - | 5.5 | - | - | 86.5 |
| Comparative example 2 | 8 | 5.5 | - | - | - | - | 86.5 |
| Example 2 | 8 | 3.0 | 2.5 | - | - | - | 86.5 |
| Example 3 | 8 | 3.0 | 1.0 | 1.5 | - | - | 86.5 |
| Example 4 | 8 | 3.0 | - | - | 2.5 | - | 86.5 |
| Example 5 | 8 | 3.0 | - | - | - | 2.5 | 86.5 |
Note: the catalyst compositions are shown in weight percent in table 1.
TABLE 2
Claims (7)
1. The catalyst for preparing isobutene comprises a carrier, an active component and an auxiliary agent, and is characterized in that: the catalyst takes at least one of MCF and SAPO molecular sieves as a carrier, vanadium as an active component, Sb and rare earth metals as auxiliaries, and the rare earth metals are Ce and Nd; the mass percentage of vanadium is V2O50.6-29% in terms of weight; the mass percentage of Sb is Sb2O50.1-5 percent of the rare earth metal, and the mass percentage of the rare earth metal is 0.3-5.0 percent of the rare earth trivalent oxide.
2. A method of preparing the catalyst of claim 1, comprising the steps of:
1) mixing the required amount of the carrier with the vanadium-containing solution and the auxiliary agent-containing solution in sequence, or mixing the required amount of the carrier with the vanadium-containing solution and the auxiliary agent-containing solution simultaneously;
2) and roasting to obtain the catalyst.
3. The method according to claim 2, wherein the calcination temperature is 550 to 850%oC。
4. The method according to claim 2, wherein the calcination time is 2 to 10 hours.
5. The method of claim 2, wherein a drying step is provided between step 1) and step 2).
6. The method according to claim 5, wherein the drying temperature is 90 to 140%oC。
7. The catalyst of claim 1 is applied to the reaction of preparing isobutene by dehydrogenating isobutane in a carbon dioxide atmosphere.
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| CN101773850A (en) * | 2010-01-28 | 2010-07-14 | 清华大学 | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof |
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| CN104549415A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenizing light alkane and using method of catalyst |
| CN104549219A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Supported catalyst for preparing olefin by dehydrogenating isobutane and application of supported catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101773850A (en) * | 2010-01-28 | 2010-07-14 | 清华大学 | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof |
| CN103121919A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation method in presence of mild oxidant |
| CN104549415A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenizing light alkane and using method of catalyst |
| CN104549219A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Supported catalyst for preparing olefin by dehydrogenating isobutane and application of supported catalyst |
Non-Patent Citations (2)
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