CN105582953A - Catalyst used for preparing butadiene through butene oxidative dehydrogenation, and application thereof - Google Patents
Catalyst used for preparing butadiene through butene oxidative dehydrogenation, and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst used for preparing butadiene through butene oxidative dehydrogenation, and an application thereof. With existing catalyst for preparing butadiene through butene oxidative dehydrogenation, butane in a butene raw material should be separated, and the conversion rates of the three isomers 1-butene, cis-2-butene and trans-2-butene under a same reaction condition are different, such that butadiene yield is not high. According to the catalyst and the application provided by the invention, the catalyst is composed of divalent metal ferrite Me II Fe2O4 and an oxide of a metal M, wherein the divalent metal Me II is at least one selected from Zn, Mg, Mn, Co, Ni and Cu. M is at least one selected from Fe, Cr, V, Sb, Sn, Ga, and In. With the technical scheme, the problem is well solved. A butadiene product can be highly efficiently, continuously and stably prepared. The catalyst and the application can be applied in industrial productions for preparing butadiene through butene oxidative dehydrogenation.
Description
Technical field
The present invention relates to a kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene and uses thereof.
Background technology
1,3-butadiene is the important monomer of the important source material of petrochemical industry, especially synthetic rubber, resin etc., in petrochemical industry olefin feedstock, has consequence. At present, the main production method of butadiene is to adopt extraction process extracting from naphtha steam cracking product C-4-fraction to obtain, and the industrial method that also adopted butane or butylene dehydrogenation is produced butadiene. Because alkane is more stable, butane dehydrogenation technological reaction temperature is higher, and accessory substance is more, and butylene is more active, and butylene oxidation-dehydrogenation reaction temperature is lower, selectively higher, has the industrialized advantage that is easy to.
In recent years, along with the fast development of synthetic rubber and resin industry, and butadiene purposes is more and more extensive, causes the market demand sustainable growth of butadiene, and butadiene raw material is comparatively in short supply. Butadiene mainly obtains by the extracting of naphtha pyrolysis product at present, can not meet the need of market far away, and the exploitation of emerging energy field Coal Chemical Industry and extensive shale gas all can not provide product butadiene. Therefore people start to pay close attention to other method for producing butadiene, particularly butylene oxidation-dehydrogenation technology. In refinery's C-4-fraction, contain a large amount of n-butenes, use added value lower as domestic fuel, butylene highly selective is converted into butadiene and has significant economic benefit, Oxidative Dehydrogenation of Butene Into Butadiene is significant for the comprehensive utilization of C-4-fraction resource.
The catalyst of exploitation high activity, high selectivity and high stability is the key of butylene oxidation-dehydrogenation technology. Ferrate catalyst based on having spinel structure is reported (CN1088624C, CN1072110 and CN1184705 etc.) by many sections of patents, the catalyst that the catalyst of this ferrite composition with spinel structure can react for butylene oxidation-dehydrogenation with the interaction of gaseous oxygen by oxonium ion in the oxidation-reduction process of iron ion and lattice. Auxiliary component in formation spinel structure in cationic type and catalyst has remarkable impact to catalyst performance, and known zinc ferrite, magnesium ferrite, Manganese Ferrite etc. show good catalytic activity in n-butene oxidative dehydrogenation. But these catalyst are generally had relatively high expectations to butene feedstock, more responsive to the normal butane content in raw material, in the time that in raw material, normal butane content is higher, catalytic activity reduces, catalyst is also easy to inactivation, thereby need to separate in advance butenes/butanes hybrid C 4 raw material. In addition, active incomplete same between butylene isomer, ferrate catalyst is higher to the reactivity of 2-butylene, lower to 1-butylene activity, and when mixture that to cause when charging be butylene isomer, butylene total conversion is on the low side. And the physical property such as 1-butylene and cis-2-butene, three kinds of isomers boiling points of Trans-2-butene approach, be difficult to separate, limit the commercial Application of Oxidative Dehydrogenation of Butene into Butadiene technology. Chinese patent (CN101980992A) utilizes Mo-Bi catalyst to have 1-butylene activity compared with high and lower to the reactivity of 2-butylene feature, adopt the method for ferrate catalyst and Mo-Bi catalyst dual bed catalyst to realize the applicability to isomer mixture in butene feedstock, but increase the complexity of technique and operation, and two kinds of catalyst of different nature need to react under identical conditions, reaction condition restriction is more. Therefore the effective catalyst that, need to develop a kind of preparing butadiene with butylene oxo-dehydrogenation that can be used for hybrid C 4 raw material is for industrial production.
Summary of the invention
Technical problem to be solved by this invention is that the existing catalyst for Oxidative Dehydrogenation of Butene into Butadiene need to separate in advance to the butane of butene feedstock, and 1-butylene and cis-2-butene to differential responses activity, three kinds of isomers of Trans-2-butene conversion ratio under same reaction conditions is different and cause the problem that butadiene yield is not high, a kind of new catalyst for Oxidative Dehydrogenation of Butene into Butadiene is provided, this method for preparing catalyst is easy, be suitable for the C4 mixture that comprises three kinds of isomers containing normal butane and n-butene as butene feedstock, there is catalytic activity high, butadiene is selectively high, the advantage that catalyst performance stabilised is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene, comprises following component:
A) with the ferrite Me of divalent metalⅡFe2O4For key component, divalent metal MeⅡBe selected from least one in Zn, Mg, Mn, Co, Ni, Cu;
B) taking the oxide of at least one element in Fe, Cr, V, Sb, Sn, Ga, In as auxiliary agent, MeⅡFe2O4With the mol ratio of each auxiliary element be 1:(0.01～1).
In technique scheme, described butene feedstock is that wherein the volume content of normal butane is less than 40% containing the hybrid C 4 raw material of n-butene and normal butane; In butene feedstock, contain at least two kinds in 1-butylene and cis-2-butene, three kinds of isomers of Trans-2-butene; Described MeⅡFe2O4In, divalent metal MeⅡBe selected from least one in Zn, Mg, Mn, Co, Ni, Cu, preferred version is at least one in Zn, Mg, Mn, Ni; Auxiliary element is selected from least one in Fe, Cr, V, Sb, Sn, Ga, In, and preferred version is at least one in Cr, V, Sb, In; MeⅡFe2O4With the mol ratio of each auxiliary element be 1:(0.01～1), preferred version is 1:(0.05～0.5).
A kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene involved in the present invention can adopt coprecipitation preparation, comprises following steps:
A) preparation is containing the mixed solution of catalytic component fully stirring;
B) co-precipitation under suitable pH value by described mixed solution and alkaline solution;
C) precipitated product washed, be dried, roasting, moulding.
In technique scheme, the component precursor of catalyst can be selected from the one in chloride or nitrate; Precipitation process pH value is 6～12, and wash temperature is 10 DEG C～80 DEG C, and baking temperature is 90 DEG C～150 DEG C, and be 1～24 hour drying time, and sintering temperature is 400 DEG C～650 DEG C, and roasting time is 1～24 hour; Aqueous slkali is selected from the one in ammoniacal liquor, NaOH or potassium hydroxide, and preferred version is ammoniacal liquor, and ammonia concn is preferably 10%～30%.
Catalyst involved in the present invention application in Oxidative Dehydrogenation of Butene into Butadiene, can adopt and comprise following processing step:
Taking the gaseous mixture of butylene, oxygen-containing gas, steam as raw material, oxygen-containing gas is air, oxygen or both mixtures, butylene in reactant: oxygen: the volume ratio of steam is 1:(0.5～5): (2～20), steam can reduce the dividing potential drop of reactant butylene, and suppresses and eliminate catalyst surface to form carbon distribution. Inlet temperature is 300 DEG C～500 DEG C, and butylene mass space velocity is 1.0～6.0h-1, raw material obtains butadiene with after catalyst haptoreaction.
Compared with prior art, the present invention has significant advantage and high-lighting effect. According to Lattice Oxygen reaction mechanism, the ferrite of spinel structure can provide butylene oxidation active sites in Oxidative Dehydrogenation of Butene into Butadiene reaction, but himself activates the scarce capacity of oxygen species, and some metal oxide has the ability of stronger activation oxygen species, utilize the cooperative effect of two-phase, catalyst demonstrates good performance. But catalyst is generally comparatively responsive to butane raw material, easily affects catalytic activity, and different and cause butadiene overall yield not high to 1-butylene and cis-2-butene, three kinds of isomers of Trans-2-butene conversion ratio under same reaction conditions. The present invention is by adding the ion that can participate in forming spinel structure ferrite to regulate butylene oxidation active sites. Add cation to there is the oxide of the metal of sky or full d track, to strengthen the ability of activation oxygen, make catalyst all there is stronger catalytic oxidative dehydrogenation performance to three kinds of butylene isomers. And add suitable modifying element and regulate the ratio of each component, strengthen the stability of catalyst to normal butane, adapt to the requirement of butenes/butanes hybrid C 4 raw material. This method for preparing catalyst is easy, be suitable for the C4 mixture that comprises three kinds of isomers containing normal butane and n-butene as butene feedstock, have catalytic activity high, butadiene is selectively high, the advantage that catalyst performance stabilised is high, has reduced the cost of butylene oxidation-dehydrogenation process.
Butylene oxidation-dehydrogenation reaction is carried out on the miniature catalyst reaction device of continuous-flow quartz tube reactor. Product analysis adopts HP-5890 gas chromatograph (HP-AL/S capillary column, 50m × 0.53mm × 15 μ m; Fid detector) alkane in on-line analysis dehydrogenation product, alkene, butadiene etc. content and calculate the conversion ratio of reaction, selective and yield. The catalyst that uses method provided by the invention to prepare reacts for butylene oxidation-dehydrogenation, butane total conversion reach or higher than 80%, butadiene selectively reaches 95%, catalyst performance is better and stability is high, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 128.0g magnesium nitrate (Mg (NO3)2·6H2O), 74.0g zinc nitrate (Zn (NO3)2·6H2O), 62.7g manganese nitrate (Mn (NO3)2·4H2O), 23.4g ammonium metavanadate (NH4VO3), 45.2g antimony chloride (SbCl3) and 30.1g indium nitrate (In (NO3)3) be dissolved in 4L deionized water, stir, form solution. Then above-mentioned solution and 20% ammonia spirit are carried out to co-precipitation, precipitation pH value remains on 9.5, and precipitation temperature is room temperature, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst A, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst A is Fe2Mg0.5Zn0.25Mn0.25V0.2Sb0.2In0.1, all the other are oxygen.
Get 0.5g catalyst A and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 1.
Table 1*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 81.8 | 95.2 |
| Cis-2-butene | 26 | 81.0 | 95.3 |
| 1-butylene | 20 | 80.4 | 95.2 |
| Butylene (total) | 76 | 81.2 | 95.2 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 2]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 204.8g magnesium nitrate (Mg (NO3)2·6H2O), 29.6g zinc nitrate (Zn (NO3)2·6H2O), 25.6g manganese nitrate (Mn (NO3)2·4H2O), 1.2g ammonium metavanadate (NH4VO3), 2.3g antimony chloride (SbCl3) and 3.0g indium nitrate (In (NO3)3) be dissolved in 4L deionized water, stir, form solution. Then above-mentioned solution and 10% ammonia spirit are carried out to co-precipitation, precipitation pH value remains on 6.0, and precipitation temperature is 10 DEG C, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 90 DEG C dry 24 hours. Dried sample again in Muffle furnace at 400 DEG C roasting within 24 hours, obtain catalyst B, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst B is Fe2Mg0.8Zn0.1Mn0.1V0.01Sb0.01In0.01, all the other are oxygen.
Get 0.5g catalyst B and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 2.
Table 2*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 74.6 | 91.7 |
| Cis-2-butene | 26 | 74.2 | 91.8 |
| 1-butylene | 20 | 73.4 | 91.5 |
| Butylene (total) | 76 | 74.1 | 91.7 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 3]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 25.6g magnesium nitrate (Mg (NO3)2·6H2O), 236.8g zinc nitrate (Zn (NO3)2·6H2O), 25.6g manganese nitrate (Mn (NO3)2·4H2O), 117.0g ammonium metavanadate (NH4VO3), 225.8g antimony chloride (SbCl3) and 300.9g indium nitrate (In (NO3)3) be dissolved in 4L deionized water, stir, form solution. Then above-mentioned solution and 30% ammonia spirit are carried out to co-precipitation, precipitation pH value remains on 12, and precipitation temperature is 80 DEG C, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 150 DEG C dry 1 hour. Dried sample again in Muffle furnace at 650 DEG C roasting within 1 hour, obtain catalyst C, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst C is Fe2Mg0.1Zn0.8Mn0.1V1Sb1In1, all the other are oxygen.
Get 0.5g catalyst C and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 3.
Table 3*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 |
| Trans-2-butene | 30 | 82.4 | 91.6 |
| Cis-2-butene | 26 | 82.0 | 91.5 |
| 1-butylene | 20 | 81.2 | 91.5 |
| Butylene (total) | 76 | 82.0 | 91.5 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 4]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 64.0g magnesium nitrate (Mg (NO3)2·6H2O), 74.0g zinc nitrate (Zn (NO3)2·6H2O), 125.5g manganese nitrate (Mn (NO3)2·4H2O), 5.8g ammonium metavanadate (NH4VO3), 11.3g antimony chloride (SbCl3) and 15.0g indium nitrate (In (NO3)3) be dissolved in 4L deionized water, stir, form solution. Then catalyst precursor solution and 15% ammonia spirit are carried out to co-precipitation, precipitation pH value remains on 8.0, and precipitation temperature is 40 DEG C, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst D, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst D is Fe2Mg0.25Zn0.25Mn0.5V0.05Sb0.05In0.05, all the other are oxygen.
Get 0.5g catalyst D and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 4.
Table 4*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 76.5 | 91.9 |
| Cis-2-butene | 26 | 76.2 | 91.5 |
| 1-butylene | 20 | 75.4 | 91.6 |
| Butylene (total) | 76 | 76.1 | 91.7 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 5]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 64.0g magnesium nitrate (Mg (NO3)2·6H2O), 148.0g zinc nitrate (Zn (NO3)2·6H2O), 62.8g manganese nitrate (Mn (NO3)2·4H2O), 58.5g ammonium metavanadate (NH4VO3), 112.9g antimony chloride (SbCl3) and 150.4g indium nitrate (In (NO3)3) be dissolved in 4L deionized water, stir, form solution. Then catalyst precursor solution and 25% ammonia spirit are carried out to co-precipitation, precipitation pH value remains on 10.0, and precipitation temperature is 60 DEG C, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst E, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst E is Fe2Mg0.25Zn0.5Mn0.25V0.5Sb0.5In0.5, all the other are oxygen.
Get 0.5g catalyst E and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 5.
Table 5*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 82.1 | 92.7 |
| Cis-2-butene | 26 | 81.6 | 92.6 |
| 1-butylene | 20 | 81.2 | 92.4 |
| Butylene (total) | 76 | 81.7 | 92.6 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 6]
Weigh 888.8g ferric nitrate (Fe (NO3)3·9H2O), 125.0g manganese nitrate (Mn (NO3)2·4H2O), 145.0g cobalt nitrate (Co (NO3)2·6H2O), 80.0g chromic nitrate (Cr (NO3)3·9H2And 25.5g gallium nitrate (Ga (NO O)3)3) be dissolved in 4L deionized water, stir, form solution. Then above-mentioned solution and 1MNaOH solution are carried out to co-precipitation, precipitation pH value remains on 9.5, and precipitation temperature is room temperature, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst F, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst F is Fe2.2Mn0.5Co0.5Cr0.2Ga0.1, all the other are oxygen.
Get 0.5g catalyst F and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 6.
Table 6*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 80.7 | 93.1 |
| Cis-2-butene | 26 | 80.5 | 93.3 |
| 1-butylene | 20 | 79.9 | 93.3 |
| Butylene (total) | 76 | 80.4 | 93.2 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 7]
Weigh 321.6g iron chloride (FeCl3), 64.0 nickel chloride (NiCl2), 66.4g copper chloride (CuCl2), 23.4g ammonium metavanadate (NH4VO3), 70.0g stannic chloride (SnCl4·5H2And 21.9g inidum chloride (InCl O)3) be dissolved in 4L deionized water, stir, form solution. Then above-mentioned solution and 2MNaOH are carried out to co-precipitation, precipitation pH value remains on 9.5, and precipitation temperature is room temperature, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst G, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst G is Fe2Ni0.5Cu0.5V0.2Sn0.2In0.1, all the other are oxygen.
Get 0.5g catalyst G and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 7.
Table 7*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 81.1 | 93.7 |
| Cis-2-butene | 26 | 80.7 | 93.6 |
| 1-butylene | 20 | 80.3 | 93.4 |
| Butylene (total) | 76 | 80.8 | 93.6 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 8]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 148.0g zinc nitrate (Zn (NO3)2·6H2O), 62.7g manganese nitrate (Mn (NO3)2·4H2O), 72.5g nickel nitrate (Ni (NO3)2·6H2O), 80.0g chromic nitrate (Cr (NO3)3·9H2O), 45.2g antimony chloride (SbCl3) and 70.0g stannic chloride (SnCl4·5H2O) be dissolved in 4L deionized water, stir, form solution. Then above-mentioned solution and 2MKOH solution are carried out to co-precipitation, precipitation pH value remains on 9.5, and precipitation temperature is room temperature, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst H, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst H is Fe2Zn0.5Mn0.25Ni0.25Cr0.2Sb0.2Sn0.2, all the other are oxygen.
Get 0.5g catalyst H and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 8.
Table 8*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 81.7 | 94.8 |
| Cis-2-butene | 26 | 81.1 | 94.9 |
| 1-butylene | 20 | 80.4 | 95.0 |
| Butylene (total) | 76 | 81.2 | 94.9 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 9]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 296.0g zinc nitrate (Zn (NO3)2·6H2And 23.4g ammonium metavanadate (NH O)4VO3) be dissolved in 4L deionized water, stir, form solution. Then above-mentioned solution and 3MKOH solution are carried out to co-precipitation, precipitation pH value remains on 9.5, and precipitation temperature is room temperature, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst I, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst I is Fe2Zn1V0.2, all the other are oxygen.
Get 0.5g catalyst I and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 9.
Table 9*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 82.1 | 90.9 |
| Cis-2-butene | 26 | 81.6 | 90.9 |
| 1-butylene | 20 | 80.7 | 91.1 |
| Butylene (total) | 76 | 81.6 | 91.0 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 10]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 64.0g magnesium nitrate (Mg (NO3)2·6H2O), 74.0g zinc nitrate (Zn (NO3)2·6H2O), 62.7g manganese nitrate (Mn (NO3)2·4H2O), 72.5g nickel nitrate (Ni (NO3)2·6H2O), 80.0g chromic nitrate (Cr (NO3)3·9H2O), 23.4g ammonium metavanadate (NH4VO3), 45.2g antimony chloride (SbCl3), 30.1g indium nitrate (In (NO3)3) and 4.3g cerous nitrate (Ce (NO3)3·6H2O) be dissolved in 4L deionized water, stir, form solution. Then above-mentioned solution and 20% ammonia spirit are carried out to co-precipitation, precipitation pH value remains on 9.5, and precipitation temperature is room temperature, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L deionized water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst J, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst J is Fe2Mg0.25Zn0.25Mn0.25Ni0.25Cr0.2V0.2Sb0.2In0.1Ce0.01, all the other are oxygen.
Get 0.5g catalyst J and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 10. Do not affect catalyst performance a small amount of adding of Ce element.
Table 10*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 81.8 | 94.5 |
| Cis-2-butene | 26 | 81.2 | 94.6 |
| 1-butylene | 20 | 80.4 | 94.6 |
| Butylene (total) | 76 | 81.2 | 94.6 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 11]
Get 0.5g catalyst A and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, air and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 component and reaction result are listed in table 11.
Table 11*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 10 | ||
| Trans-2-butene | 36 | 81.9 | 95.3 |
| Cis-2-butene | 28 | 81.2 | 95.2 |
| 1-butylene | 26 | 80.7 | 95.3 |
| Butylene (total) | 90 | 81.3 | 95.3 |
* the butene conversion and the butadiene that react 10 hours are selective
[embodiment 12]
Get 0.5g catalyst A and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, air and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 12.
Table 12*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 15 | ||
| Trans-2-butene | 45 | 81.8 | 95.3 |
| 1-butylene | 40 | 80.6 | 95.2 |
| Butylene (total) | 85 | 81.2 | 95.3 |
* the butene conversion and the butadiene that react 10 hours are selective
[comparative example 1]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 148.0g zinc nitrate (Zn (NO3)2·6H2And 128.0g magnesium nitrate (Mg (NO O)3)2·6H2O) be dissolved in 4L distilled water, stir, form solution. Then above-mentioned solution and 20% ammonia spirit are carried out to co-precipitation, precipitation pH value remains on 9.5, and precipitation temperature is room temperature, then with centrifugal separator, the solid sample in precipitated product is separated, with 4L distilled water washing, by gained solid in baking oven 110 DEG C dry 4 hours. Dried sample again in Muffle furnace at 600 DEG C roasting within 4 hours, obtain catalyst K, grind to form 40～60 order particles for evaluating catalyst. The element composition molar ratio of catalyst K is Fe2Zn0.5Mg0.5, all the other are oxygen.
Get 0.5g catalyst K and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 13.
Table 13*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Trans-2-butene | 41 | 71.2 | 90.1 |
| Cis-2-butene | 32 | 68.4 | 89.2 |
| 1-butylene | 27 | 60.7 | 85.1 |
| Butylene (total) | 100 | 67.5 | 88.6 |
* the butene conversion and the butadiene that react 10 hours are selective
[comparative example 2]
Get 0.5g catalyst K and carry out butylene oxidation-dehydrogenation evaluation. Feeding gas is C4 mixture, oxygen and steam, wherein n-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, first steam, oxygen and C4 mixture is fully mixed, then is incorporated into and in reactor, carries out oxidative dehydrogenation. Reactor inlet temperatures is 340 DEG C; Reaction pressure is normal pressure; N-butene mass space velocity is 5h-1. Under above-mentioned condition, carry out after catalytic reaction, product is analyzed by gas chromatography. In reactant, the composition of C4 mixture and reaction result are listed in table 14.
Table 14*
| Composition | Volume content | Butene conversion (%) | Butadiene selective (%) |
| Normal butane | 24 | ||
| Trans-2-butene | 30 | 65.2 | 87.3 |
| Cis-2-butene | 26 | 62.4 | 87.0 |
| 1-butylene | 20 | 54.7 | 85.3 |
| Butylene (total) | 76 | 61.5 | 86.7 |
* the butene conversion and the butadiene that react 10 hours are selective.
Claims (10)
1. for a catalyst for Oxidative Dehydrogenation of Butene into Butadiene, comprise following component:
A) with the ferrite Me of divalent metalⅡFe2O4For key component, divalent metal MeⅡBe selected from Zn, Mg, Mn, Co,At least one in Ni, Cu;
B) taking the oxide of at least one element in Fe, Cr, V, Sb, Sn, Ga, In as auxiliary agent, MeⅡFe2O4WithThe mol ratio of each auxiliary element is 1:(0.01～1).
2. according to claim 1 for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is characterized in that described butyleneRaw material is the mixture of n-butene and normal butane.
3. according to claim 1 for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is characterized in that described butyleneRaw material is containing at least two kinds in 1-butylene and cis-2-butene, Trans-2-butene.
4. according to claim 1 for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is characterized in that described divalenceMetal M eⅡBe selected from least one in Zn, Mg, Mn, Ni.
5. according to claim 1 for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is characterized in that described auxiliary agentElement is selected from least one in Cr, V, Sb, In.
6. according to claim 1 for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is characterized in that described MeⅡFe2O4With the mol ratio of each auxiliary element be 1:(0.05～0.5).
7. according to claim 1 for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is characterized in that catalystPreparation adopts coprecipitation, comprises following steps:
A) preparation is containing the mixed solution of catalytic component fully stirring;
B) co-precipitation under suitable pH value by described mixed solution and alkaline solution;
C) precipitated product washed, be dried, roasting, moulding.
8. according to claim 7 for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is characterized in that precipitation processPH value is 6～12, and wash temperature is 10 DEG C～80 DEG C, and baking temperature is 90 DEG C～150 DEG C, and be 1～24 drying timeHour, sintering temperature is 400 DEG C～650 DEG C, roasting time is 1～24 hour.
9. according to claim 7 for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is characterized in that aqueous slkali choosingOne in ammoniacal liquor, NaOH or potassium hydroxide.
10. for the application of the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, with butylene, air or oxygen, steamGaseous mixture be raw material, reaction inlet temperature is 300 DEG C～500 DEG C, butylene mass space velocity is 1.0～6.0h-1, raw material is with powerProfit requires to obtain butadiene after the catalyst haptoreaction described in 1～9 any one.
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| CN107537533A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Catalyst and its process for Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions |
| CN108602734A (en) * | 2016-06-30 | 2018-09-28 | 环球油品公司 | Pass through the oxidative dehydrogenation method that then direct dehydrogenation produces butadiene |
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| CN112569973A (en) * | 2019-09-27 | 2021-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene, preparation method and application thereof |
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