CN106607031B - Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and application thereof - Google Patents
Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing butadiene through oxidative dehydrogenation of butylene and application thereof, and mainly solves the problems that the existing catalyst for preparing butadiene through oxidative dehydrogenation of butylene is low in butadiene selectivity and low in catalyst stability. The invention relates to a catalyst for preparing butadiene by oxidative dehydrogenation of butylene and application thereof, wherein the catalyst component contains Fe3+And W element, wherein Fe3+With Fe2O3Or Fe2O4 2‑The mass content of Na element in the catalyst is less than 900ppm, the mass content of K element is less than 900ppm, and the mass content of Ba element is less than 900ppm, so that the problem is solved well, the butadiene product is prepared efficiently and stably, the generation of reaction by-products is reduced, the stability of the catalyst is high, and the catalyst can be used in the industrial production of butadiene through oxidative dehydrogenation of butylene.
Description
Technical Field
The invention relates to a catalyst for preparing butadiene by oxidative dehydrogenation of butylene and application thereof.
Background
1, 3-butadiene is an important monomer for synthetic rubber, resin, and the like, and plays an important role in petrochemical olefin raw materials. In recent years, with the rapid development of the synthetic rubber and resin industry and the wider and wider application of butadiene, the market demand of butadiene is continuously increased, and the butadiene raw material is in short supply. At present, butadiene is mainly extracted from naphtha cracking products and can not meet market demands, but the development of coal chemical industry and large-scale shale gas in the emerging energy field can not provide butadiene products, so people begin to pay attention to other butadiene production methods, and research on butylene oxidative dehydrogenation technology is wide. The carbon four-fraction of the refinery contains a large amount of butylene, the carbon four-fraction has low use added value as civil fuel, and the high-selectivity conversion of the butylene into butadiene has obvious economic benefit and has important significance for the comprehensive utilization of carbon four-fraction resources.
The development of a catalyst with high activity, high selectivity and high stability is the key of the butylene oxidative dehydrogenation technology, and a ferrite catalyst with a spinel structure is a better catalyst for preparing butadiene by oxidative dehydrogenation of butylene (USP3270080, CN1088624C, CN1184705 and the like), and simultaneously, α -Fe2O3Is also an important component of the iron-based catalyst for oxidative dehydrogenation of butylene. The type of cations constituting the spinel structure and the promoter content of the catalyst have a significant effect on the performance of the catalyst, and the performance of ferrite catalysts can be further modified by mixing metal oxides, introducing certain cations into the catalyst to distort the spinel structure, and adding other promoters (CN1033013A, CN1072110, etc.). However, although the processes reported in the above patents have achieved certain economic benefits in the industrial production of butadiene by oxidative dehydrogenation of butene, the selectivity of the catalyst for the target product is still not ideal enough, the amount of deep oxides in the reaction is large, and the stability of the catalyst is low. With the increasing requirements for resources and environmental protection, it is necessary to develop a catalyst with higher butadiene selectivity for the industrial production process of butadiene production by oxidative dehydrogenation of butene, and to minimize COxAnd (4) discharging. In addition, the influence of catalyst components or the introduction of trace (or small) elements during the preparation of the catalyst on the performance of the catalyst has not been studied intensively in the literature.
Disclosure of Invention
The invention aims to solve the technical problems that the existing catalyst for preparing butadiene by oxidative dehydrogenation of butylene has low selectivity to butadiene and low catalyst stability, and provides a novel catalyst for preparing butadiene by oxidative dehydrogenation of butylene.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a catalyst for preparing butadiene by oxidative dehydrogenation of butylene contains Fe3+The method is characterized in that the mass content of Na element in the catalyst is less than 900 ppm; the mass content of the K element is less than 900 ppm.
In the above technical solution, preferably, Fe is contained in the catalyst3+Is α -Fe2O3Or Fe2O4 2-At least one of (1).
In the above technical scheme, preferably, the catalyst further comprises a W element, and the mass content of the W element in the catalyst is 0.05-10%.
In the above technical scheme, the Fe2O4 2-Ferrite Me of spinel or trans-spinel structureⅡFe2O4Wherein the divalent metal MeⅡContains at least one of Zn, Mg, Mn and Ni, and preferably at least one of Zn and Mg; the mass content of the W element in the catalyst is 0.05-10%, and the preferred scheme is 0.1-5%;
in the above technical solutions, the mass content of Na element in the catalyst is preferably less than 800ppm, more preferably less than 600ppm, and most preferably less than 400 ppm.
In the above technical solutions, the content of K element in the catalyst is preferably less than 800ppm, more preferably less than 600ppm, and most preferably less than 400 ppm.
In the above technical solutions, the mass content of Ba element in the catalyst is less than 900ppm, preferably less than 800ppm, more preferably less than 600ppm, and most preferably less than 400 ppm.
The invention relates to a catalyst for preparing butadiene by oxidative dehydrogenation of butylene, which can be prepared by the following steps:
a) preparing a mixed solution containing a catalyst component and fully stirring;
b) co-precipitating the mixed solution with an alkaline solution at a suitable pH value;
c) washing, drying, roasting and molding the precipitation product.
In the above technical scheme, the component precursor of the catalyst can be selected from one of chloride or nitrate; the pH value in the precipitation process is 6-12, the washing temperature is 10-80 ℃, the drying temperature is 90-150 ℃, the drying time is 1-24 hours, the roasting temperature is 400-650 ℃, and the roasting time is 1-24 hours.
The application of the catalyst in preparing butadiene by oxidative dehydrogenation of butylene can adopt the following process steps:
the mixed gas of butylene, oxygen-containing gas and steam is used as raw materials, the temperature of a reaction inlet is 300-500 ℃, and the mass space velocity of butylene is 1.0-6.0 h-1And the raw materials are contacted with a catalyst for reaction to obtain butadiene.
Butene in the reactants: oxygen: the volume ratio of water vapor is 1: (0.5-5): (2-20), preheating water into steam before entering the reactor, and fully mixing the steam with the raw material gas.
Compared with the prior art, the invention has remarkable advantages and outstanding effects of α -Fe2O3The spinel-structured ferrite mainly provides a butylene oxidation active site in the butylene oxidative dehydrogenation reaction, and α -Fe2O3Oxygen is mainly activated. Proper amount of tungsten oxide can match the performance of the catalyst on the aspects of butylene oxidation and oxygen activation, thereby leading the catalytic performance to reach the best state, realizing high butylene conversion rate and butadiene selectivity and reducing deep oxidation product CO2Is generated. The double bond charge density of the butene is high, the butene belongs to pi alkali, and the catalyst can absorb butene molecules to react only by certain acidity. The performance of the catalyst was found to be very sensitive to the acid strength and amount at the surface of the catalyst. The surface acidity is too weak, the adsorption of reactants is less, and the conversion rate is lower; the acidity is too strong and the acid is too strong,the by-products increase significantly and the butadiene selectivity decreases. Some trace or small elements are introduced into the catalyst components or in the preparation process of the catalyst, so that the surface acidity and alkalinity of the catalyst can be changed, and the influence on the performance of the catalyst is obviously influenced. Oxides of elements such as Na, K, Ba and the like have strong alkalinity, proper acid-base matching of the catalyst is broken, and the catalyst can be seriously inactivated by the small amount of the elements. The method is obviously of great significance to the industrial application of the butadiene catalyst prepared by oxidative dehydrogenation of butylene. In the reaction process, the addition of a proper amount of water vapor can reduce the partial pressure of the reactant butylene, stabilize the reaction temperature, inhibit and eliminate carbon deposition formed on the surface of the catalyst, improve the selectivity of butadiene and play an important role in maintaining the stability of the catalyst. The catalyst has the advantages of simple preparation method, high butadiene selectivity, fewer byproducts, particularly deep oxides, and high catalyst performance stability, improves the resource utilization rate of the butylene oxidative dehydrogenation process, and reduces carbon emission.
The butylene oxidative dehydrogenation reaction is carried out on a micro catalytic reaction device of a continuous flow quartz tube reactor. Analysis of products the contents of alkane, alkene, butadiene, etc. in the dehydrogenated product were analyzed on-line using HP-5890 gas chromatograph (HP-AL/S capillary column, 50 m.times.0.53 mm.times.15 μm; FID detector) and the conversion of the reaction and the product selectivity were calculated. When the catalyst prepared by the method is used for butylene oxidative dehydrogenation, the total conversion rate of butane is 75-82%, the selectivity of butadiene is 95%, and the selectivity of deep oxidation products is low. The catalyst has good performance and high stability, and obtains good technical effect.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
A proper amount of high-purity ferric nitrate and magnesium nitrate are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then coprecipitating the above solution with 20% ammonia water solution, maintaining the pH value of the precipitate at 9.5 and the precipitation temperature at room temperature, and then centrifuging the precipitate with a centrifugal separatorA sample of the solid in the product was isolated, washed with 4L of deionized water, and the resulting solid was dried in an oven at 110 ℃ for 4 hours. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst A, and grinding the catalyst A into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of the catalyst A is Fe2O3 .2MgFe2O4The catalyst further contains, in terms of mass fraction, Na 200ppm, K200 ppm, and Ba 100 ppm.
[ example 2 ]
A proper amount of high-purity ferric nitrate and magnesium nitrate are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then, the solution and 10% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 6.0, the precipitation temperature is 10 ℃, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 24 hours at the temperature of 90 ℃. And roasting the dried sample in a muffle furnace at 400 ℃ for 24 hours to obtain a catalyst B, and grinding the catalyst B into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of the catalyst B is Fe2O3 .20MgFe2O4The catalyst further contains Na 300ppm, K100 ppm and Ba 80ppm in mass fraction.
[ example 3 ]
Appropriate amount of high-purity ferric nitrate and magnesium nitrate are weighed and mixed in 1L of deionized water, and the mixture is stirred uniformly. Then, the solution and 30% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 12, the precipitation temperature is 80 ℃, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 1 hour at 150 ℃. And roasting the dried sample in a muffle furnace at 650 ℃ for 1 hour to obtain a catalyst C, and grinding the catalyst C into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst C consisted of 20Fe2O3 .1MgFe2O4The catalyst further contains Na100ppm, K200 ppm and Ba 150ppm in mass fraction.
[ example 4 ]
Weighing a proper amount of high-purity ferric nitrate and magnesium nitrate, and mixing the mixture in 1L of deionized waterAnd stirring uniformly. Then the catalyst precursor solution and 15% ammonia solution were coprecipitated, the precipitation pH was maintained at 8.0 and the precipitation temperature was 40 ℃, then a solid sample in the precipitated product was separated with a centrifuge, washed with 4L deionized water, and the resulting solid was dried in an oven at 110 ℃ for 4 hours. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst D, and grinding the catalyst D into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst D had a composition of 1Fe2O3 .5MgFe2O4The catalyst further contains Na100ppm, K300ppm and Ba 300ppm in mass fraction.
[ example 5 ]
A proper amount of high-purity ferric nitrate and magnesium nitrate are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then the catalyst precursor solution and 25% ammonia water solution were coprecipitated, the precipitation pH was maintained at 10.0 and the precipitation temperature was 60 ℃, then a solid sample in the precipitated product was separated with a centrifuge, washed with 4L of deionized water, and the resulting solid was dried in an oven at 110 ℃ for 4 hours. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst E, and grinding the catalyst E into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst E consisted of 5Fe2O3 .1MgFe2O4The catalyst also contained Na 80ppm, K240 ppm, Ba 200ppm by mass.
[ example 6 ]
A proper amount of high-purity ferric nitrate and zinc nitrate are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst F, and grinding the catalyst F into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst F consists of 1Fe2O3 .2ZnFe2O4The catalyst also contains Na 50ppm,K 360ppm、Ba 70ppm。
[ example 7 ]
Proper amount of high-purity ferric nitrate, magnesium nitrate, zinc nitrate and antimony oxide are weighed and mixed in 1L of deionized water, and the mixture is stirred uniformly. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst G, and grinding the catalyst G into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst G had a composition of 1Fe2O3 .2MgFe2O4 .2ZnFe2O4The catalyst further contained, in mass percentage, W0.05%, Na 120ppm, K150ppm, and Ba 380 ppm.
[ example 8 ]
Appropriate amount of high-purity ferric nitrate, magnesium nitrate, manganese nitrate and antimony oxide are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst H, and grinding the catalyst H into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst H consists of 1Fe2O3 .2MgFe2O4 .2MnFe2O4The catalyst further contained, in mass percentage, W10%, Na 150ppm, K100 ppm, and Ba 120 ppm.
[ example 9 ]
Proper amount of high-purity ferric nitrate, magnesium nitrate, zinc nitrate, nickel nitrate and antimony oxide are weighed and mixed in 1L of deionized water, and the mixture is stirred uniformly. Then coprecipitating the above solution with 20% ammonia water solution, maintaining the pH value of the precipitate at 9.5 and the precipitation temperature at room temperature, separating the solid sample in the precipitate with a centrifugal separator, and separating with a filter4L of deionized water, and the resulting solid was dried in an oven at 110 ℃ for 4 hours. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst I, and grinding the catalyst I into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst I consists of 1Fe2O3 .2MgFe2O4 .2ZnFe2O4 .1NiFe2O4The catalyst further contained, in mass percentage, W2%, Na 200ppm, K300ppm, and Ba 100 ppm.
[ example 10 ]
Appropriate amount of high-purity ferric nitrate and magnesium nitrate are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst J, and grinding the catalyst J into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst J consisted of Fe2O3 .2MgFe2O4The catalyst also contained Na 450ppm, K500 ppm, Ba 550ppm by mass.
[ example 11 ]
Appropriate amount of high-purity ferric nitrate and magnesium nitrate are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst K, and grinding the catalyst K into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of the catalyst K consists of Fe2O3 .2MgFe2O4The catalyst also contained Na 700ppm, K780 ppm and Ba 650ppm in mass fraction.
[ example 12 ]
Weighing machineProper amount of high purity ferric nitrate and magnesium nitrate are mixed in 1L deionized water and stirred uniformly. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst L, and grinding the catalyst L into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst L consists of Fe2O3 .2MgFe2O4The catalyst also contains Na 850ppm, K820 ppm and Ba840ppm by mass fraction.
[ example 13 ]
Appropriate amount of high-purity ferric nitrate and magnesium nitrate are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst M, and grinding the catalyst M into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of the catalyst M consists of Fe2O3 .2MgFe2O4The catalyst also contains Na 150ppm, K300ppm, Ba 850ppm by mass.
[ example 14 ]
Appropriate amount of high-purity ferric nitrate and magnesium nitrate are weighed and mixed in 1L of deionized water, and the mixture is uniformly stirred. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst N, and grinding the catalyst N into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of the catalyst N is Fe2O3 .2MgFe2O4The catalyst also contained Na 250ppm, K820 ppm and Ba 500ppm in mass fraction.
Comparative example 1
Proper amount of ferric nitrate and magnesium nitrate with lower purity are weighed and mixed in 1L of deionized water, and the mixture is stirred uniformly. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst O, and grinding the catalyst O into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of the catalyst O is Fe2O3 .2MgFe2O4The catalyst also contained Na 1000ppm, K2000 ppm, Ba 1500ppm by mass.
Comparative example 2
Proper amount of ferric nitrate, magnesium nitrate, manganese nitrate and antimony oxide with lower purity are weighed and mixed in 1L of deionized water, and the mixture is stirred uniformly. Then, the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, 4L deionized water is used for washing, and the obtained solid is dried in an oven for 4 hours at 110 ℃. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst P, and grinding the catalyst P into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of catalyst P is 1Fe2O3 .2MgFe2O4 .2MnFe2O4The catalyst further contained, in mass percentage, W10%, Na 1200ppm, K300ppm, and Ba 600 ppm.
Comparative example 3
Proper amount of ferric nitrate and magnesium nitrate with lower purity are weighed and mixed in 1L of deionized water, and the mixture is stirred uniformly. Then coprecipitating the above solution with 20% ammonia water solution, maintaining the pH value of the precipitate at 9.5 and the precipitation temperature at room temperature, separating the solid sample from the precipitate with a centrifugal separator, washing with 4L deionized water, and collecting the solidDried in an oven at 110 ℃ for 4 hours. And roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst Q, and grinding the catalyst Q into particles of 40-60 meshes for catalyst evaluation. The Fe-containing component of the catalyst Q is Fe2O3 .2MgFe2O4The catalyst also contains Na 500ppm, K1600 ppm and Ba 1200ppm by mass fraction.
[ example 15 ]
0.5g of the catalysts A to Q were taken for the evaluation of oxidative dehydrogenation of butene. The feed gas is a mixture of butylene, oxygen and water vapor, wherein the ratio of butylene: oxygen: the composition molar ratio of water is 1: 0.75: and 10, fully mixing the raw material gases, and introducing the raw material gases into a reactor to perform oxidative dehydrogenation. The inlet temperature of the reactor is 340 ℃; the reaction pressure is normal pressure; the mass space velocity of the butylene is 5h-1. The catalytic reaction was carried out under the above conditions, and the reaction product was analyzed by gas chromatography. The reaction results are shown in Table 1.
TABLE 1
Butene conversion and butadiene selectivity over 10 hours of reaction
[ example 16 ]
0.5g of catalyst A, P was taken for the evaluation of oxidative dehydrogenation of butene. The feed gas is a mixture of butylene, oxygen and water vapor, wherein the ratio of butylene: oxygen: the composition molar ratio of water is 1: 0.75: and 10, fully mixing the raw material gases, and introducing the raw material gases into a reactor to perform oxidative dehydrogenation. The inlet temperature of the reactor is 340 ℃; the reaction pressure is normal pressure; the mass space velocity of the butylene is 5h-1. The catalytic reaction was carried out under the above conditions, and the reaction product was analyzed by gas chromatography. The reaction results are shown in Table 2.
TABLE 2
Claims (3)
1. A catalyst for preparing butadiene by oxidative dehydrogenation of butylene contains Fe3+The method is characterized in that the mass content of Na element in the catalyst is 120-300 ppm; the mass content of the element K is 100-300 ppm; the mass content of the Ba element is 80-380 ppm; the catalyst also comprises a W element, and the mass content of the W element in the catalyst is 2-5%; fe of catalyst3+Is α -Fe2O3And Fe2O4 2-。
2. The application of the catalyst for preparing butadiene by oxidative dehydrogenation of butylene is characterized in that mixed gas of butylene, oxygen-containing gas and steam is used as raw materials, the reaction inlet temperature is 300-500 ℃, and the mass space velocity of butylene is 1.0-6.0 h-1Butadiene is obtained by contacting the starting material with the catalyst of claim 1.
3. Use of a catalyst according to claim 2 for the oxidative dehydrogenation of butene to butadiene, wherein the molar ratio of butene: oxygen: the volume ratio of water vapor is 1: (0.5-5): (2-20).
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| JP2014198334A (en) * | 2013-03-13 | 2014-10-23 | 三菱化学株式会社 | Composite metal oxide catalyst and method for producing conjugated diene |
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