CN105582953B - Catalyst and application thereof for Oxidative Dehydrogenation of Butene into Butadiene - Google Patents
Catalyst and application thereof for Oxidative Dehydrogenation of Butene into Butadiene Download PDFInfo
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Abstract
The catalyst and application thereof that the present invention relates to a kind of for Oxidative Dehydrogenation of Butene into Butadiene, mainly solve to be currently used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene to need to separate the butane in butene feedstock, and to 1- butylene and three kinds of cis-2-butene, Trans-2-butene isomers conversion ratio is different under the same reaction conditions and the problem that causes butadiene yield not high.The present invention is by a kind of catalyst and application thereof for Oxidative Dehydrogenation of Butene into Butadiene, and the catalyst is with the ferrite Me of divalent metalⅡFe2O4Oxide with M metal is composition, wherein divalent metal MeⅡSelected from least one of Zn, Mg, Mn, Co, Ni and Cu, M is selected from the technical solution of at least one of Fe, Cr, V, Sb, Sn, Ga, In, preferably solves the problems, such as this, efficiently, butadiene product is continuously and stably produced, can be used in the industrial production of Oxidative Dehydrogenation of Butene into Butadiene.
Description
Technical field
The catalyst and application thereof that the present invention relates to a kind of for Oxidative Dehydrogenation of Butene into Butadiene.
Background technique
1,3-butadiene is the important monomer of the important source material of petrochemical industry, especially synthetic rubber, resin etc., in petrochemical industry
There is consequence in olefin feedstock.Currently, the main production process of butadiene is to be split using extraction process from naphtha steam
It extracts and obtains in solution product C-4-fraction, butane or the method for butylene dehydrogenation was industrially also used to produce butadiene.Due to alkane
Hydrocarbon is more stable, and butane dehydrogenation technological reaction temperature is higher, and by-product is more, and butylene is more active, and butylene oxidation-dehydrogenation is anti-
Answer temperature lower, selectivity is higher, has and is easy to industrialized advantage.
In recent years, as the fast development of synthetic rubber and resin industry and butadiene purposes are more and more extensive, cause
The market demand sustainable growth of butadiene, butadiene raw material are more in short supply.Butadiene mainly passes through naphtha pyrolysis product at present
Extracting obtains, and has been far from satisfying the market demand, and the exploitation of emerging energy field coal chemical industry and extensive shale gas is all
Product butadiene cannot be provided.Therefore people begin to focus on other method for producing butadiene, especially butylene oxidation-dehydrogenation technology.
Contain a large amount of n-butene in refinery's C-4-fraction, uses added value lower as domestic fuel, butylene is turned with high selectivity
Butadiene is turned to significant economic benefit, comprehensive utilization of the Oxidative Dehydrogenation of Butene Into Butadiene for C-4-fraction resource
It is of great significance.
Develop high activity, highly selective and high stability catalyst is the key that butylene oxidation-dehydrogenation technology.Based on tool
There is the ferrate catalyst of spinel structure to report (CN1088624C, CN1072110 and CN1184705 by numerous patents
Deng), the catalyst of this ferrite composition with spinel structure can pass through the oxidation-reduction process and crystalline substance of iron ion
The catalyst that oxonium ion is reacted with the interaction of gaseous oxygen for butylene oxidation-dehydrogenation in lattice.Constitute spinel structure middle-jiao yang, function of the spleen and stomach from
The type of son and the auxiliary component in catalyst, which have catalyst performance, to be significantly affected, it is known that zinc ferrite, magnesium ferrite, ferrous acid
Manganese etc. shows preferable catalytic activity in n-butene oxidative dehydrogenation.But these catalyst are generally to butene feedstock requirement
Higher, more sensitive to the normal butane content in raw material, when normal butane content is higher in raw material, catalytic activity is reduced, catalyst
It is also easy to inactivate, thus needs to mix C4 raw material to butenes/butanes and be pre-separated.In addition, active between butylene isomer
Not exactly the same, ferrate catalyst is higher to the reactivity of 2- butylene, lower to 1- butylene activity, causes to feed as fourth
When the mixture of alkene isomer, butylene total conversion is relatively low.And 1- butylene and three kinds of cis-2-butene, Trans-2-butene isomers boilings
The physical property such as point are close, are difficult to separate, limit the industrial application of Oxidative Dehydrogenation of Butene into Butadiene technology.Chinese patent
(CN101980992A) have using Mo-Bi catalyst higher and lower to the reactivity of 2- butylene to 1- butylene activity
Feature is realized mixed to isomers in butene feedstock using the method for ferrate catalyst and Mo-Bi catalyst dual bed catalyst
The applicability of object is closed, but increases the complexity of technique and operation, and two kinds of catalyst of different nature are needed in same
It is reacted under part, reaction condition limitation is more.Therefore, it is necessary to develop a kind of butylene oxidation-dehydrogenation that can be used for mixing C4 raw material
The effective catalyst of butadiene is prepared for industrial production.
Summary of the invention
The technical problem to be solved by the present invention is to be currently used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene needs pair
Butane in butene feedstock is pre-separated, and to the active 1- butylene of differential responses and cis-2-butene, Trans-2-butene
Three kinds of isomers conversion ratio is different under the same reaction conditions and the problem that causes butadiene yield not high, a kind of new use is provided
In the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, the method for preparing catalyst is easy, is applicable in and contains normal butane and n-butene packet
The C4 mixture of three kinds of isomers is included as butene feedstock, has catalytic activity high, butadiene selective is high, and catalyst performance is steady
Qualitative high advantage.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of be used for Oxidative Dehydrogenation of Butene
The catalyst of butadiene includes following components:
A) with the ferrite Me of divalent metalⅡFe2O4For main component, divalent metal MeⅡSelected from Zn, Mg, Mn, Co, Ni,
At least one of Cu；
B) using the oxide of at least one of Fe, Cr, V, Sb, Sn, Ga, In element as auxiliary agent, MeⅡFe2O4With each auxiliary agent
The molar ratio of element is 1:(0.01~1).
In above-mentioned technical proposal, the butene feedstock is the mixing C4 raw material containing n-butene and normal butane, wherein normal butane
Volume content less than 40%；In butene feedstock in butylene containing 1- and three kinds of cis-2-butene, Trans-2-butene isomers at least
Two kinds；The MeⅡFe2O4In, divalent metal MeⅡSelected from least one of Zn, Mg, Mn, Co, Ni, Cu, preferred embodiment Zn,
At least one of Mg, Mn, Ni；Auxiliary element is selected from least one of Fe, Cr, V, Sb, Sn, Ga, In, and preferred embodiment is
At least one of Cr, V, Sb, In；MeⅡFe2O4Molar ratio with each auxiliary element is 1:(0.01~1), preferred embodiment 1:
(0.05~0.5).
Coprecipitation preparation can be used in a kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to the present invention,
It comprises the steps of:
A) it prepares the mixed solution containing catalytic component and is sufficiently stirred；
B) mixed solution and alkaline solution are co-precipitated under suitable pH value；
C) precipitated product washed, dried, roasted, formed.
In above-mentioned technical proposal, the component precursor of catalyst can be selected from one of chloride or nitrate；Precipitation process
PH value is 6~12, and wash temperature is 10 DEG C~80 DEG C, and drying temperature is 90 DEG C~150 DEG C, and drying time is 1~24 hour,
Maturing temperature is 400 DEG C~650 DEG C, and calcining time is 1~24 hour；Aqueous slkali is selected from ammonium hydroxide, sodium hydroxide or potassium hydroxide
One of, preferred embodiment is ammonium hydroxide, and ammonia concn is preferably 10%~30%.
Application of the catalyst according to the present invention in Oxidative Dehydrogenation of Butene into Butadiene, can be used comprising following technique
Step:
Using butylene, oxygen-containing gas, vapor gaseous mixture as raw material, oxygen-containing gas be air, oxygen or both mixing
Object, butylene in reactant: oxygen: the volume ratio of vapor is 1:(0.5~5): (2~20), vapor can reduce reactant fourth
The partial pressure of alkene, and inhibit and eliminate catalyst surface formation carbon distribution.Inlet temperature is 300 DEG C~500 DEG C, and butylene mass space velocity is
1.0~6.0h-1, raw material is with obtaining butadiene after catalyst haptoreaction.
Compared with prior art, the present invention has the advantages that significant and high-lighting effect.According to Lattice Oxygen reaction mechanism, point
The ferrite of spinel structure can provide butylene oxidation active sites in Oxidative Dehydrogenation of Butene into Butadiene reaction, but its own is activated
The scarce capacity of oxygen species, and certain metal oxides have the ability of stronger activation oxygen species, are imitated using the collaboration of two-phase
It answers, catalyst shows preferable performance.But catalyst is generally more sensitive to butane raw material, is easy to influence catalytic activity, with
And conversion ratio is different and cause fourth two under the same reaction conditions to 1- butylene and three kinds of cis-2-butene, Trans-2-butene isomers
Alkene overall yield is not high.The present invention may participate in the ion to form spinel structure ferrite by addition and be lived with adjusting butylene oxidation
Property position.Cation is added, and there is the oxide of the metal of empty or full d track to make catalyst to enhance the ability of activating oxygen
All there is stronger catalytic oxidative dehydrogenation performance to three kinds of butylene isomers.And modifying element appropriate is added and adjusts each group
The ratio divided, enhancing catalyst adapt to the requirement of butenes/butanes mixing C4 raw material to the stability of normal butane.The catalyst system
Preparation Method is easy, be applicable in containing normal butane and n-butene include three kinds of isomers C4 mixture as butene feedstock, with urging
It is high to change activity, butadiene selective is high, the high advantage of catalyst performance stabilised, reduce butylene oxidation-dehydrogenation process at
This.
Butylene oxidation-dehydrogenation reaction carries out on the continuously flowing miniature catalyst reaction device of quartz tube reactor.Product analysis
Using HP-5890 gas chromatograph (HP-AL/S capillary column, 50m × 0.53mm × 15 μm；Fid detector) on-line analysis is de-
The content of alkane, alkene, butadiene in hydrogen product etc. and conversion ratio, selectivity and the yield for calculating reaction.Use this hair
The catalyst of the method preparation of bright offer is reacted for butylene oxidation-dehydrogenation, and butane total conversion reaches at or above 80%, fourth two
For alkene selectivity up to 95%, catalyst performance is preferable and stability is high, achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 128.0g magnesium nitrate (Mg (NO3)2·6H2O), 74.0g nitric acid
Zinc (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, it stirs evenly, forms solution.It then will be above-mentioned molten
Liquid is co-precipitated with 20% ammonia spirit, and precipitating pH value is maintained at 9.5, and precipitation temperature is room temperature, then uses centrifugal separator
Solid sample in precipitated product is separated, is washed with 4L deionized water, by obtained solid 110 DEG C of dryings 4 in an oven
Hour.Sample after drying roasts 4 hours at 600 DEG C in Muffle furnace again obtains catalyst A, is ground into 40~60 mesh particles
For evaluating catalyst.The element constitutive molar ratio example of catalyst A is Fe2Mg0.5Zn0.25Mn0.25V0.2Sb0.2In0.1, remaining is
Oxygen.
0.5g catalyst A is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 2]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 204.8g magnesium nitrate (Mg (NO3)2·6H2O), 29.6g nitric acid
Zinc (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, it stirs evenly, forms solution.Then by above-mentioned solution
It is co-precipitated with 10% ammonia spirit, precipitating pH value is maintained at 6.0, and precipitation temperature is 10 DEG C, then will with centrifugal separator
Solid sample in precipitated product is separated, and is washed with 4L deionized water, and by obtained solid, 90 DEG C of dryings 24 are small in an oven
When.Sample after drying roasts 24 hours at 400 DEG C in Muffle furnace again obtains catalyst B, is ground into 40~60 mesh particles
For evaluating catalyst.The element constitutive molar ratio example of catalyst B is Fe2Mg0.8Zn0.1Mn0.1V0.01Sb0.01In0.01, remaining is
Oxygen.
0.5g catalyst B is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 3]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 25.6g magnesium nitrate (Mg (NO3)2·6H2O), 236.8g nitric acid
Zinc (Zn (NO3)2·6H2O), 25.6g manganese nitrate (Mn (NO3)2·4H2O), 117.0g ammonium metavanadate (NH4VO3), 225.8g chlorination
Antimony (SbCl3) and 300.9g indium nitrate (In (NO3)3) be dissolved in 4L deionized water, it stirs evenly, forms solution.It then will be above-mentioned
Solution is co-precipitated with 30% ammonia spirit, and precipitating pH value is maintained at 12, and precipitation temperature is 80 DEG C, then uses centrifugal separator
Solid sample in precipitated product is separated, is washed with 4L deionized water, by obtained solid 150 DEG C of dryings 1 in an oven
Hour.Sample after drying roasts 1 hour at 650 DEG C in Muffle furnace again obtains catalyst C, is ground into 40~60 mesh particles
For evaluating catalyst.The element constitutive molar ratio example of catalyst C is Fe2Mg0.1Zn0.8Mn0.1V1Sb1In1, remaining is oxygen.
0.5g catalyst C is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 4]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 64.0g magnesium nitrate (Mg (NO3)2·6H2O), 74.0g nitric acid
Zinc (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, it stirs evenly, forms solution.Then by catalyst
Precursor solution is co-precipitated with 15% ammonia spirit, and precipitating pH value is maintained at 8.0, and precipitation temperature is 40 DEG C, then with centrifugation
Seperator separates the solid sample in precipitated product, is washed with 4L deionized water, by 110 DEG C in an oven of obtained solid
It is 4 hours dry.Sample after drying roasts 4 hours at 600 DEG C in Muffle furnace again obtains catalyst D, is ground into 40~60
Mesh particle is used for evaluating catalyst.The element constitutive molar ratio example of catalyst D is Fe2Mg0.25Zn0.25Mn0.5V0.05Sb0.05In0.05,
Remaining is oxygen.
0.5g catalyst D is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 5]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 64.0g magnesium nitrate (Mg (NO3)2·6H2O), 148.0g nitric acid
Zinc (Zn (NO3)2·6H2O), 62.8g manganese nitrate (Mn (NO3)2·4H2O), 58.5g ammonium metavanadate (NH4VO3), 112.9g chlorination
Antimony (SbCl3) and 150.4g indium nitrate (In (NO3)3) be dissolved in 4L deionized water, it stirs evenly, forms solution.It then will catalysis
Agent precursor solution is co-precipitated with 25% ammonia spirit, and precipitating pH value is maintained at 10.0, and precipitation temperature is 60 DEG C, then with from
Centrifugal separator separates the solid sample in precipitated product, is washed with 4L deionized water, by obtained solid in an oven 110
DEG C dry 4 hours.Sample after drying roasts 4 hours at 600 DEG C in Muffle furnace again obtains catalyst E, it is ground into 40~
60 mesh particles are used for evaluating catalyst.The element constitutive molar ratio example of catalyst E is Fe2Mg0.25Zn0.5Mn0.25V0.5Sb0.5In0.5,
Remaining is oxygen.
0.5g catalyst E is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 6]
Weigh 888.8g ferric nitrate (Fe (NO3)3·9H2O), 125.0g manganese nitrate (Mn (NO3)2·4H2O), 145.0g nitre
Sour cobalt (Co (NO3)2·6H2O), 80.0g chromic nitrate (Cr (NO3)3·9H2) and 25.5g gallium nitrate (Ga (NO O3)3) it is dissolved in 4L
It in ionized water, stirs evenly, forms solution.Then above-mentioned solution and 1M NaOH solution are co-precipitated, precipitating pH value is kept
9.5, precipitation temperature is room temperature, is then separated the solid sample in precipitated product with centrifugal separator, with 4L go from
Sub- water washing, by obtained solid 110 DEG C drying 4 hours in an oven.Sample after drying roasts at 600 DEG C in Muffle furnace again
It burns 4 hours and obtains catalyst F, be ground into 40~60 mesh particles for evaluating catalyst.The element constitutive molar ratio example of catalyst F
For Fe2.2Mn0.5Co0.5Cr0.2Ga0.1, remaining is oxygen.
0.5g catalyst F is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 7]
Weigh 321.6g iron chloride (FeCl3), 64.0 nickel chloride (NiCl2), 66.4g copper chloride (CuCl2), the inclined vanadium of 23.4g
Sour ammonium (NH4VO3), 70.0g stannic chloride (SnCl4·5H2) and 21.9g inidum chloride (InCl O3) be dissolved in 4L deionized water, it stirs
Uniformly, solution is formed.Then above-mentioned solution and 2M NaOH are co-precipitated, precipitating pH value is maintained at 9.5, and precipitation temperature is
Then solid sample in precipitated product is separated with centrifugal separator, is washed with 4L deionized water, gained is consolidated by room temperature
Body 110 DEG C drying 4 hours in an oven.Sample after drying roasts 4 hours at 600 DEG C in Muffle furnace again obtains catalyst
G is ground into 40~60 mesh particles for evaluating catalyst.The element constitutive molar ratio example of catalyst G is
Fe2Ni0.5Cu0.5V0.2Sn0.2In0.1, remaining is oxygen.
0.5g catalyst G is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 8]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 148.0g zinc nitrate (Zn (NO3)2·6H2O), 62.7g nitric acid
Manganese (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 it) is dissolved in 4L deionized water, stirs evenly, form solution.Then
Above-mentioned solution and 2M KOH solution are co-precipitated, precipitating pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation
Seperator separates the solid sample in precipitated product, is washed with 4L deionized water, by 110 DEG C in an oven of obtained solid
It is 4 hours dry.Sample after drying roasts 4 hours at 600 DEG C in Muffle furnace again obtains catalyst H, is ground into 40~60
Mesh particle is used for evaluating catalyst.The element constitutive molar ratio example of catalyst H is Fe2Zn0.5Mn0.25Ni0.25Cr0.2Sb0.2Sn0.2,
Remaining is oxygen.
0.5g catalyst H is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 9]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 296.0g zinc nitrate (Zn (NO3)2·6H2O) and 23.4g is inclined
Ammonium vanadate (NH4VO3) be dissolved in 4L deionized water, it stirs evenly, forms solution.Then by above-mentioned solution and 3M KOH solution into
Row co-precipitation, precipitating pH value are maintained at 9.5, and precipitation temperature is room temperature, then with centrifugal separator by the solid in precipitated product
Sample is separated, and is washed with 4L deionized water, by obtained solid 110 DEG C drying 4 hours in an oven.Sample after drying is again
It is roasted 4 hours at 600 DEG C in Muffle furnace and obtains catalyst I, be ground into 40~60 mesh particles for evaluating catalyst.Catalysis
The element constitutive molar ratio example of agent I is Fe2Zn1V0.2, remaining is oxygen.
0.5g catalyst I is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 10]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 64.0g magnesium nitrate (Mg (NO3)2·6H2O), 74.0g nitric acid
Zinc (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 it) is dissolved in 4L deionized water, stirs evenly, form solution.It then will be above-mentioned
Solution is co-precipitated with 20% ammonia spirit, and precipitating pH value is maintained at 9.5, and precipitation temperature is room temperature, then uses centrifugal separator
Solid sample in precipitated product is separated, is washed with 4L deionized water, 110 DEG C of dryings 4 are small in an oven by obtained solid
When.Sample after drying roasts 4 hours at 600 DEG C in Muffle furnace again obtains catalyst J, is ground into 40~60 mesh particles and is used for
Evaluating catalyst.The element constitutive molar ratio example of catalyst J is Fe2Mg0.25Zn0.25Mn0.25Ni0.25Cr0.2V0.2Sb0.2In0.1Ce0.01,
Remaining is oxygen.
0.5g catalyst J is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture are listed in table 10.The addition of a small amount of Ce element does not influence catalyst performance.
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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 11]
0.5g catalyst A is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, air and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 component 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[embodiment 12]
0.5g catalyst A is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, air and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[comparative example 1]
Weigh 808.0g ferric nitrate (Fe (NO3)3·9H2O), 148.0g zinc nitrate (Zn (NO3)2·6H2) and 128.0g nitre O
Sour magnesium (Mg (NO3)2·6H2O it) is dissolved in 4L distilled water, stirs evenly, form solution.Then by above-mentioned solution and 20% ammonium hydroxide
Solution is co-precipitated, and precipitating pH value is maintained at 9.5, and precipitation temperature is room temperature, then will be in precipitated product with centrifugal separator
Solid sample separate, water washing is distilled with 4L, by obtained solid 110 DEG C drying 4 hours in an oven.Sample after drying
Product roast 4 hours at 600 DEG C in Muffle furnace obtain catalyst K again, are ground into 40~60 mesh particles for evaluating catalyst.
The element constitutive molar ratio example of catalyst K is Fe2Zn0.5Mg0.5, remaining is oxygen.
0.5g catalyst K is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted
[comparative example 2]
0.5g catalyst K is taken to carry out butylene oxidation-dehydrogenation evaluation.Feeding gas be C4 mixture, oxygen and vapor, wherein
N-butene: oxygen: the constitutive molar ratio of water is 1:0.75:10, is first sufficiently mixed vapor, oxygen and C4 mixture,
It is re-introduced into reactor and carries out oxidative dehydrogenation.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；N-butene
Mass space velocity is 5h-1.After carrying out catalysis reaction under above-mentioned condition, reaction product is analyzed with gas chromatography.In reactant
The composition and reaction result of C4 mixture 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 |
* 10 hours butene conversions and butadiene selectives are reacted.
Claims (9)
1. a kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene includes following components:
A) with the ferrite Me of divalent metalⅡFe2O4For main component, divalent metal MeⅡIn Zn, Mg, Mn, Co, Ni, Cu
At least one；
B) using the oxide of at least one of Cr, V, Sb, Sn, Ga, In element as auxiliary agent, MeⅡFe2O4With each auxiliary element
Molar ratio is 1:(0.01~1)；
The butene feedstock is the mixture of n-butene and normal butane.
2. being used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that the butylene is former
Expect at least two in butylene containing 1- and cis-2-butene, Trans-2-butene.
3. being used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that the divalent gold
Belong to MeⅡSelected from least one of Zn, Mg, Mn, Ni.
4. being used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that the auxiliary agent member
Element is selected from least one of Cr, V, Sb, In.
5. being used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that the MeⅡFe2O4
Molar ratio with each auxiliary element is 1:(0.05~0.5).
6. being used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that the system of catalyst
It is standby to use coprecipitation comprising the steps of:
A) it prepares the mixed solution containing catalytic component and is sufficiently stirred；
B) mixed solution and alkaline solution are co-precipitated under suitable pH value；
C) precipitated product washed, dried, roasted, formed.
7. being used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 6, it is characterised in that precipitation process pH
Value is 6~12, and wash temperature is 10 DEG C~80 DEG C, and drying temperature is 90 DEG C~150 DEG C, and drying time is 1~24 hour, roasting
Temperature is 400 DEG C~650 DEG C, and calcining time is 1~24 hour.
8. being used for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene according to claim 6, it is characterised in that aqueous slkali is selected from
One of ammonium hydroxide, sodium hydroxide or potassium hydroxide.
9. a kind of application of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene, with butylene, air or oxygen, vapor it is mixed
Conjunction gas is raw material, and reaction inlet temperature is 300 DEG C~500 DEG C, and butylene mass space velocity is 1.0~6.0h-1, raw material is with claim
Butadiene is obtained after 1~8 described in any item catalyst haptoreactions.
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| CN107537530B (en) * | 2016-06-29 | 2020-02-04 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and process method thereof |
| CN107537533B (en) * | 2016-06-29 | 2019-08-02 | 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 |
| CN111054363A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene |
| CN111054347A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for oxidation of butene |
| CN111054348A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Process for producing butadiene |
| CN111054351A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for producing butadiene by oxidative dehydrogenation of butylene |
| CN112239391B (en) * | 2019-07-16 | 2023-08-04 | 中国石油化工股份有限公司 | Method for preparing 1,3-butadiene by butene dehydrogenation |
| 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 |
| CN112691678A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and preparation method thereof |
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