CN107537530B - Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and process method thereof - Google Patents
Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and process method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing butadiene by oxidative dehydrogenation of butylene and a process method thereof, which mainly solve the problems of high steam unit consumption, large wastewater generation amount and high energy consumption in the existing production process for preparing butadiene by oxidative dehydrogenation of butylene. The invention relates to a catalyst for preparing butadiene by butylene oxidative dehydrogenation and a process method thereof, wherein the catalyst uses ferrous acid salt Me of divalent metalⅡFe2O4Is a main active component, wherein the divalent metal MeⅡAt least one selected from Zn, Mg, Ni and Co, and BiPO4Or SnO2At least one of the above-mentioned materials and VIIB group element oxide are used as adjuvant, and the catalyst precursor and deionized water are prepared according to a certain mole ratio, and passed through the processes of precipitation, washing, drying, roasting and forming so as to obtain the invented catalyst.
Description
Technical Field
The invention relates to a catalyst for preparing butadiene by oxidative dehydrogenation of butylene and a process method thereof.
Background
1, 3-butadiene is an important monomer for chemical products such as synthetic rubber and resin, 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 process route for producing butadiene by oxidative dehydrogenation of butylene has great application prospect.
The oxidative dehydrogenation of butene is a strongly exothermic reaction, and in order to achieve a good catalytic effect, a large amount of water vapor needs to be mixed into a reaction raw material to be used as a diluent gas and a heat carrier.
The Oxo-D process of the American TPC group (formerly Texas Petrochemical) and the O-X-D process of Philips are typical processes for preparing butadiene through oxidative dehydrogenation of butene. The Oxo-D process adopts a ferrite catalyst, and the molar ratio of water vapor to butylene is 10: 1.
the processes for preparing butadiene by oxidative dehydrogenation of butylene, which have been used for industrial production in China, mainly comprise an adiabatic fixed bed reaction process adopting a B-02 iron-based catalyst and a fluidized bed reaction process adopting an H-198 iron-based catalyst as a representative. B-02 adiabatic fixed bed process employed a steam to butene molar ratio of about 16: 1.
the existing production process for preparing butadiene by oxidative dehydrogenation of butylene has high steam unit consumption, large wastewater generation amount and high energy consumption, and the amount of steam needs to be reduced as much as possible along with the improvement of the requirements on environmental protection, energy conservation and emission reduction. However, the current relevant patent literature reports that the research on the low water ratio catalyst for preparing butadiene by oxidative dehydrogenation of butene has less mention. The development of high-activity and low-water-ratio catalysts is the key of the low-water-ratio and low-energy-consumption butylene oxidative dehydrogenation technology. Ferrite catalysts based on spinel structure are the better catalysts for the oxidative dehydrogenation of butene to butadiene (USP3270080, CN1088624C, CN1072110, CN1184705, etc.). The type of cations in the spinel structure and the additive components in the catalyst have a significant effect on the performance of the catalyst, and the performance of the ferrite catalyst can be further modified by mixing metal oxides, introducing certain cations into the catalyst to distort the spinel structure, adding other additives, and the like. The water vapor has the function of carrying out hydration reaction with the surface of the ferrite catalyst during the oxidative dehydrogenation reaction of the butylene so as to activate the catalyst. Therefore, the appropriate components with better hydrophilicity are added into the catalyst, so that the utilization efficiency of the water vapor can be improved, the consumption of the water vapor is reduced, and the purposes of energy conservation and emission reduction are achieved.
Disclosure of Invention
The invention aims to solve the technical problems of high steam unit consumption, large waste water generation amount and high energy consumption in the existing production process of preparing butadiene by oxidative dehydrogenation of butylene, 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 comprises the following components:
a) ferrous acid salt Me of divalent metalsⅡFe2O4As a main component, a divalent metal MeⅡAt least one selected from Zn, Mg, Ni and Co;
b) taking an oxide of a VIIB group element as an auxiliary agent, wherein the molar ratio of the VIIB group element to the Fe element is (0-1): 10;
c) with BiPO4Or SnO2At leastIs an auxiliary agent, namely BiPO4Or the molar ratio of Sn to Fe is (0.01-1): 10;
d) the method comprises the following steps of taking an oxide of lanthanide as an auxiliary agent, wherein the molar ratio of the lanthanide to Fe is (0-1): 10.
in the above technical solution, MeⅡFe2O4Middle, divalent metal MeⅡAt least one selected from Zn, Mg, Ni and Co, preferably at least one selected from Zn and Mg; the VIIB group element is selected from at least one of Mn and Re, and the preferred molar ratio of the VIIB group element to the Fe element is (0.01-1): 10, more preferably (0.05-0.5): 10; BiPO4Or the molar ratio of Sn to Fe is (0.05-0.5): 10; the lanthanide is selected from at least one of La, Ce or Nd, preferably at least one of La or Ce, and the molar ratio of the lanthanide to the Fe is preferably (0.01-1): 10, more preferably (0.05-0.5): 10.
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 alkaline solution is selected from one of ammonia water, sodium hydroxide or potassium hydroxide, wherein the ammonia water is the best, and the concentration of the ammonia water is preferably 10-30%.
The application of the catalyst in preparing butadiene by oxidative dehydrogenation of butylene can adopt the following process steps:
using the mixed gas of butylene, air or oxygen and water vapor as raw materials, and the reaction inlet temperature is 300The temperature is 500 ℃ below zero, and the mass airspeed of the 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: (0.5-4): (2-10), preheating water into steam before entering the reactor, and fully mixing the steam with the raw material gas.
In the above technical scheme, butene: the volume ratio of the water vapor is preferably 1: (3-8), and the more preferable scheme is 1: (5-8).
The catalyst of the invention can be used in a fixed bed or fluidized bed reactor.
Compared with the prior art, the invention has obvious advantages and outstanding effects. The catalyst composed of ferrite with a spinel structure is used for catalyzing the reaction of preparing butadiene by oxidative dehydrogenation of butylene, and shows better performance, but the selectivity of butadiene is not high enough, and a higher water-olefin ratio is needed to achieve proper catalytic performance. The invention provides surface acidity suitable for butylene adsorption and butadiene desorption by adding auxiliary agents such as ions which can participate in forming spinel-structured ferrite to adjust butylene oxidation active sites and adding proper modification auxiliary agents to adjust the surface acidity of the catalyst. And a proper component with better hydrophilicity is added into the catalyst, so that the utilization efficiency of the water vapor can be improved, the consumption of the water vapor is reduced, and the purposes of energy conservation and emission reduction are achieved. The catalyst has the advantages of simple preparation method, high butadiene selectivity and high catalyst activity stability, reduces the unit consumption of steam and the generation amount of wastewater, and reduces the energy consumption.
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. The catalyst prepared by the method is used for butylene oxidative dehydrogenation, the conversion rate of butylene is close to 80%, the selectivity of butadiene is higher than 90%, and high performance can be maintained under the condition of low water-olefin ratio. 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 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 640.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 740.0g of zinc nitrate (Zn (NO)3)2·6H2O), 62.7g of manganese nitrate (Mn (NO)3)2·4H2O), 60.8g of bismuth phosphate (BiPO)4) And 86.8g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. 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 A, and grinding the catalyst A into particles of 40-60 meshes for catalyst evaluation. The molar ratio of the element composition of the catalyst A is Fe10.0Mg2.5Zn2.5Mn0.25Bi0.2P0.2Ce0.2And the balance of oxygen.
[ example 2 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 1150.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 148.0g of zinc nitrate (Zn (NO)3)2·6H2O), 2.6g of manganese nitrate (Mn (NO)3)2·4H2O), 3.1g of bismuth phosphate (BiPO)4) And 4.34g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. 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 ℃. The dried sample was then applied to a horseRoasting the mixture for 24 hours at 400 ℃ in a muffle furnace to obtain a catalyst B, and grinding the catalyst B into particles of 40-60 meshes for catalyst evaluation. The molar ratio of the element composition of the catalyst B is Fe10.0Mg4.5Zn0.5Mn0.01Bi0.01P0.01Ce0.01And the balance of oxygen.
[ example 3 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 128.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 1332.0g of zinc nitrate (Zn (NO)3)2·6H2O), 256.0g of manganese nitrate (Mn (NO)3)2·4H2O), 304.0g of bismuth phosphate (BiPO)4) And 433.9g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. 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 molar ratio of the element composition of the catalyst C is Fe10.0Mg0.5Zn4.5Mn1.0Bi1.0P1.0Ce1.0The balance being oxygen.
[ example 4 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 640.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 740.0g of zinc nitrate (Zn (NO)3)2·6H2O), 12.5g of manganese nitrate (Mn (NO)3)2·4H2O), 15.2g of bismuth phosphate (BiPO)4) And 21.7g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. Then coprecipitating the catalyst precursor solution with 15% ammonia water solution, maintaining the pH value of the precipitate at 8.0 and the precipitation temperature at 40 ℃, and then separating out the solid sample in the precipitate product by using a centrifugal separatorWashed 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 D, and grinding the catalyst D into particles of 40-60 meshes for catalyst evaluation. The elemental composition of catalyst D was Fe in a molar ratio10.0Mg2.5Zn2.5Mn0.05Bi0.05P0.05Ce0.05And the balance of oxygen.
[ example 5 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 640.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 740.0g of zinc nitrate (Zn (NO)3)2·6H2O), 125.5g of manganese nitrate (Mn (NO)3)2·4H2O), 152.0g of bismuth phosphate (BiPO)4) And 217.0g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. 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 molar ratio of the element composition of the catalyst E is Fe10.0Mg2.5Zn2.5Mn0.5Bi0.5P0.5Ce0.5And the balance of oxygen.
[ example 6 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 1280.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 73.1g rhenium chloride (ReCl)3) 70.1 tin chloride (SnCl)4·5H2O) and 86.6g lanthanum nitrate (La (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. Then the solution is coprecipitated with 2M NaOH, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, and then a centrifugal separator is used for separating the solid in the precipitateThe sample 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 F, and grinding the catalyst F into particles of 40-60 meshes for catalyst evaluation. The molar ratio of the element composition of the catalyst F is Fe10.0Mg5.0Re0.25Sn0.2La0.2And the balance of oxygen.
[ example 7 ]
1608.4g of ferric chloride (FeCl) were weighed3) 1480.0g of Zinc nitrate (Zn (NO)3)2·6H2O), 73.1g rhenium chloride (ReCl)3) 70.1g of tin chloride (SnCl)4·5H2O) and 86.6g lanthanum nitrate (La (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. Then the solution and 2M KOH solution are coprecipitated, the precipitation pH value is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitation 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 molar ratio of the element composition of the catalyst G is Fe10.0Zn5.0Re0.25Sn0.2La0.2And the balance of oxygen.
[ example 8 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 1454g nickel nitrate (Ni (NO)3)2·6H2O), 62.7g of manganese nitrate (Mn (NO)3)2·4H2O), 73.1g rhenium chloride (ReCl)3) 70.1g of tin chloride (SnCl)4·5H2O) and 87.7g of neodymium nitrate (Nd (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. Then the solution and 3M KOH solution are coprecipitated, the precipitation pH value is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitation 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 ℃. After dryingAnd roasting the 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 molar ratio of the element composition of the catalyst H is Fe10.0Ni5.0Mn0.25Re0.25Sn0.2Nd0.2And the balance of oxygen.
[ example 9 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 640.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 727.5g of cobalt nitrate (Co (NO)3)2·6H2O), 62.7g of manganese nitrate (Mn (NO)3)2·4H2O), 73.1g rhenium chloride (ReCl)3) 70.1g of tin chloride (SnCl)4·5H2O) and 86.8g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. 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 I, and grinding the catalyst I into particles of 40-60 meshes for catalyst evaluation. The molar ratio of the elements of the catalyst I is Fe10.0Mg2.5Co2.5Mn0.25Re0.25Sn0.2Ce0.2And the balance of oxygen.
[ example 10 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 640.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 740.0g of zinc nitrate (Zn (NO)3)2·6H2O), 62.7g of manganese nitrate (Mn (NO)3)2·4H2O), 73.1g rhenium chloride (ReCl)3) 70.1g of tin chloride (SnCl)4·5H2O), 86.8g of cerium nitrate (Ce (NO)3)3·6H2O) and 86.6g lanthanum nitrate (La (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. Then will be atThe solution is coprecipitated with 20% ammonia water solution, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate 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 molar ratio of the element composition of the catalyst J is Fe10.0Mg2.5Zn2.5Mn0.25Re0.25Sn0.2Ce0.2La0.2And the balance of oxygen.
[ example 11 ]
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 640.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 740.0g of zinc nitrate (Zn (NO)3)2·6H2O), 60.8g of bismuth phosphate (BiPO)4) And 70.1g of tin chloride (SnCl)4·5H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. 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 molar ratio of the element composition of the catalyst K is Fe10.0Mg2.5Zn2.5Bi0.2P0.2Sn0.2And the balance of oxygen.
[ example 12 ]
4444.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 640.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 727.0g of nickel nitrate (Ni (NO)3)2·6H2O), 62.7g of manganese nitrate (Mn (NO)3)2·4H2O), 73.1g rhenium chloride (ReCl)3) 60.8g of bismuth phosphate (BiPO)4) 70.1g of tin chloride (SnCl)4·5H2O) and 86.8g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. 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 molar ratio of the element composition of the catalyst L is Fe11.0Mg2.5Ni2.5Mn0.25Re0.25Bi0.2P0.2Sn0.2Ce0.2And the balance of oxygen.
Comparative example 1
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 640.0g of magnesium nitrate (Mg (NO)3)2·6H2O), 740.0g of zinc nitrate (Zn (NO)3)2·6H2O) was dissolved in 4L of distilled water and stirred well to form a solution. Then, the above solution was coprecipitated with a 20% aqueous ammonia solution, the pH of the precipitate was maintained at 9.5, the precipitation temperature was room temperature, then a solid sample in the precipitated product was separated by a centrifugal separator, washed with 4L of distilled 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 M, and grinding the catalyst M into particles of 40-60 meshes for catalyst evaluation. The molar ratio of the element composition of the catalyst M is Fe10.0Zn2.5Mg2.5And the balance of oxygen.
Comparative example 2
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 1479.9g of zinc nitrate (Zn (NO)3)2·6H2O) and 62.7g of manganese nitrate (Mn (NO)3)2·4H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. Then coprecipitating the solution and 20% ammonia water solution, keeping the pH value of the precipitate at 9.5 and the precipitation temperature at room temperature, then separating out the solid sample in the precipitate product by a centrifugal separator,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 N, and grinding the catalyst N into particles of 40-60 meshes for catalyst evaluation. The element composition molar ratio of the catalyst N is Fe10.0Zn5.0Mn0.25And the balance of oxygen.
Comparative example 3
4040.0g of iron nitrate (Fe (NO) were weighed3)3·9H2O), 1479.9g of zinc nitrate (Zn (NO)3)2·6H2O) and 86.8g of cerium nitrate (Ce (NO)3)3·6H2O) is dissolved in 4L of deionized water and stirred uniformly to form a solution. 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 molar ratio of the elements of the catalyst O is Fe10.0Zn5.0Ce0.2And the balance of oxygen.
[ example 13 ]
0.5g of the catalysts A to O 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 6, fully mixing the raw material gases, and introducing the raw material gases into the 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 14 ]
0.5g of catalyst A, M 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 6, fully mixing the raw material gases, and introducing the raw material gases into the 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
[ example 15 ]
0.5g of catalyst A, M 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: the oxygen is in a molar ratio of 1: 0.75, water: the composition molar ratio of butene is shown in Table 3, and the raw material gases were first mixed thoroughly and then introduced into the reactor for 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 3.
Claims (10)
1. A catalyst for preparing butadiene by oxidative dehydrogenation of butylene comprises the following components:
a) ferrous acid salt Me of divalent metalsⅡFe2O4As a main component, a divalent metal MeⅡAt least one selected from Zn, Mg, Ni and Co;
b) taking an oxide of a VIIB group element as an auxiliary agent, wherein the molar ratio of the VIIB group element to the Fe element is (0-1): 10;
c) with BiPO4Or SnO2At least one of them is an auxiliary agent, the BiPO4Or the molar ratio of Sn to Fe is (0.01-1): 10;
d) the method comprises the following steps of taking an oxide of lanthanide as an auxiliary agent, wherein the molar ratio of the lanthanide to Fe is (0-1): 10;
wherein the lanthanide is selected from at least one of La, Ce or Nd.
2. Catalyst for the oxidative dehydrogenation of butene to butadiene according to claim 1, characterized in that said divalent metal MeⅡAt least one selected from Zn, Mg, Ni and Co.
3. Catalyst for the oxidative dehydrogenation of butene to butadiene according to claim 2, characterized in that said divalent metal MeⅡAt least one selected from Zn and Mg.
4. The catalyst for preparing butadiene by oxidative dehydrogenation of butene according to claim 1, wherein the VIIB element is at least one selected from Mn and Re, and the molar ratio of the VIIB element to the Fe element is (0.05-0.5): 10.
5. the catalyst for the oxidative dehydrogenation of butene to butadiene according to claim 1, wherein said BiPO is4Or the molar ratio of Sn to Fe is (0.05-0.5): 10.
6. the catalyst for preparing butadiene by oxidative dehydrogenation of butene according to claim 1, wherein the molar ratio of lanthanide element to Fe element is (0.05-0.5): 10.
7. the catalyst for preparing butadiene by oxidative dehydrogenation of butene according to claim 1, wherein the preparation method of the catalyst comprises 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.
8. The catalyst for preparing butadiene through oxidative dehydrogenation of butene according to claim 7, wherein the pH value during 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.
9. 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-1A butadiene obtained by a contact reaction of a raw material with the catalyst according to any one of claims 1 to 8.
10. Use of a catalyst according to claim 9 for the oxidative dehydrogenation of butene to butadiene, wherein the molar ratio of butene: oxygen: the volume ratio of water vapor is 1: (0.5-4): (2-10).
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| CN103551157A (en) * | 2013-11-14 | 2014-02-05 | 中国石油大学(北京) | Method for preparing rare-earth modified zinc-iron composite oxide catalyst and application of catalyst in reaction of preparing butadiene from butene |
| CN105582953A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst used for preparing butadiene through butene oxidative dehydrogenation, and application thereof |
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