CN106607064A - Catalyst for butene oxidative dehydrogenation preparation of butadiene and application thereof - Google Patents
Catalyst for butene oxidative dehydrogenation preparation of butadiene and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for butene oxidative dehydrogenation preparation of butadiene and an application thereof. The catalyst mainly solves the problem that the existing catalyst for butene oxidative dehydrogenation preparation of butadiene has low selectivity to butadiene and produces more oxygen-containing by-products. The catalyst component comprises Fe<3+> and Os elements, wherein Fe<3+> exists in at least one form of Fe2O3 and Fe2O4<2->, Cs mass content of the catalyst is less than 900ppm, Al mass content of the catalyst is less than 900ppm and P mass content of the catalyst is less than 900ppm. The catalyst solves the problem, realizes efficient and stable preparation of a butadiene product, reduces oxygen-containing by-products and can be used for industrial production of butadiene through butene oxidative dehydrogenation.
Description
Technical field
The present invention relates to a kind of catalyst and its application for Oxidative Dehydrogenation of Butene into Butadiene.
Background technology
1,3-butadiene is the important monomer of synthetic rubber, resin etc., has consequence in petrochemical industry olefin feedstock.Closely
Nian Lai, as the fast development of synthetic rubber and resin industry, and butadiene purposes are more and more extensive, causes butadiene
Market demand sustainable growth, butadiene raw material is more in short supply.At present butadiene is mainly obtained by the extracting of naphtha pyrolysis product,
The market demand far can not have been met, and the exploitation of emerging energy field Coal Chemical Industry and extensive shale gas can not all provide fourth
Diene products, therefore people begin to focus on other method for producing butadiene, wherein to the research of butylene oxidation-dehydrogenation technology more
Extensively.Contain substantial amounts of butylene in refinery's C-4-fraction, use added value relatively low as domestic fuel, by butylene high selectivity
Be converted into butadiene there is significant economic benefit, it 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.Based on point
The ferrate catalyst of spinel structure be Oxidative Dehydrogenation of Butene into Butadiene better catalyst (USP3270080,
CN1088624C and CN1184705 etc.).Meanwhile, α-Fe2O3It is also the important component of butylene oxidation-dehydrogenation Fe-series catalyst.
The auxiliary component in the type and catalyst of spinel structure cationic is constituted on catalyst performance with significantly affecting, is led to
Cross mixed-metal oxides, some cations are introduced into catalyst so that spinel structure is distorted and adds other helps
The methods such as agent can also further modulation ferrate catalyst performance (CN1033013A and CN1072110 etc.).However, to the greatest extent
The method of pipe above patent report achieves certain economic benefit in the industrial production of Oxidative Dehydrogenation of Butene into Butadiene, but
The target product selectivity of catalyst is still not ideal enough, and the oxygen-containing accessory substance in reaction is more.With resource, environmental protection will
The raising asked, needs industrial processes exploitation the urging with higher butadiene selective for Oxidative Dehydrogenation of Butene into Butadiene
Agent, while reducing CO as far as possiblexDischarge.Additionally, introduce in catalytic component, or catalyst preparation process it is micro (or
Impact of the element to catalyst performance on a small quantity) is not also furtherd investigate by document.
The content of the invention
The technical problem to be solved is that the catalyst for being currently used for Oxidative Dehydrogenation of Butene into Butadiene is selected butadiene
Selecting property is not high, produce the more problem of oxygen-containing accessory substance, there is provided a kind of new catalysis for Oxidative Dehydrogenation of Butene into Butadiene
Agent, the method for preparing catalyst is easy, the generation of oxygen-containing accessory substance is reduced in butylene oxidation-dehydrogenation reaction, with fourth two
Alkene is selective high, accessory substance is particularly that deep oxidation thing is less, the advantage that catalyst performance stabilised is high.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows：One kind is used for Oxidative Dehydrogenation of Butene fourth two
The catalyst of alkene, includes Fe in component3+, it is characterised in that the mass content of Cs elements is less than 900ppm in catalyst；Al
The mass content of element is less than 900ppm.
In above-mentioned technical proposal, it is preferable that Fe in catalyst3+For α-Fe2O3Or Fe2O4 2-In at least one.
In above-mentioned technical proposal, it is preferable that Os elements, Os elements mass content in the catalyst are also included in catalyst
For 0.05～10%.
In above-mentioned technical proposal, the Fe2O4 2-For spinel structure or the ferrite Me of inverse spinel structureⅡFe2O4,
Divalent metal Me thereinⅡComprising at least one in Zn, Mg, Mn, Ni, preferred version be in Zn, Mg extremely
Few one kind；Os elements mass content in the catalyst is 0.05～10%, and preferred version is 0.1～5%；
In above-mentioned technical proposal, the preferred version of the mass content of Cs elements is less than 800ppm, more preferably just in catalyst
Case is that most preferably scheme is less than 400ppm less than 600ppm.
In above-mentioned technical proposal, the preferred version of the mass content of Al elements is less than 800ppm, more preferably just in catalyst
Case is that most preferably scheme is less than 400ppm less than 600ppm.
In above-mentioned technical proposal, in catalyst the mass content of P element be less than 900ppm, preferred version be less than 800ppm,
More preferably scheme is that most preferably scheme is less than 400ppm less than 600ppm.
A kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene involved in the present invention, can be prepared using following steps：
A) prepare the mixed solution containing catalytic component and be sufficiently stirred for；
B) mixed solution and alkaline solution are co-precipitated under suitable pH value；
C) precipitated product is washed, is dried, roasting, shaping.
In above-mentioned technical proposal, the component precursor of catalyst may be selected from chloride or the one kind in nitrate；Precipitation process pH
It is worth for 6～12, wash temperature is 10 DEG C～80 DEG C, baking temperature is 90 DEG C～150 DEG C, drying time is 1～24 little
When, sintering temperature is 400 DEG C～650 DEG C, and roasting time is 1～24 hour.
The application of catalyst involved in the present invention in Oxidative Dehydrogenation of Butene into Butadiene, can adopt comprising following technique step
Suddenly：
With butylene, oxygen-containing gas, vapor gaseous mixture as raw material, reaction inlet temperature be 300 DEG C～500 DEG C, butylene matter
Amount air speed is 1.0～6.0h-1, raw material after catalyst haptoreaction with obtaining butadiene.
Butylene in reactant：Oxygen：The volume ratio of vapor is 1：(0.5～5)：(2～20), water into reactor it
It is front to be heated as vapor in advance and be sufficiently mixed with unstripped gas.
Compared with prior art, the present invention has significant advantage and high-lighting effect.With α-Fe2O3And spinel structure
Ferrite composition catalyst be used for catalyzing butene oxidative dehydrogenation butadiene react, show preferable performance.Spinelle
The ferrite of structure main offer butylene oxidation active sites in butylene oxidation-dehydrogenation reaction, and α-Fe2O3Then mainly activate oxygen
Gas.The oxide of appropriate Os can make catalyst to mutual between the performance between butylene oxidation and oxygen activating two aspect
Match somebody with somebody, so that catalytic performance reaches optimum state, realize high butene conversion and butadiene selective.The double bond electric charge of butylene
Density is higher, belongs to π alkali, and the certain acidity of catalyst needs could adsorb butylene molecule and react.Research finds, urges
The performance of agent is very sensitive to catalyst surface acid strength and quantity.Surface acidity is too weak, and reactant absorption is less, conversion
Rate is relatively low；Acidity is too strong, then accessory substance showed increased, and butadiene selective is reduced.In catalytic component, or catalyst
Some micro or oligo-elements are introduced in preparation process can change the surface acidic-basic property of catalyst, so as to significantly affect catalyst shadow
Ring performance.The oxide of the elements such as Cs, Al, P has respectively stronger surface acidic-basic property, breaks ring catalyst suitably sour
Alkalescence matching, a small amount of presence of these elements can make catalyst inactivation serious.In addition, applicants have discovered that, these elements
Addition be also possible to hinder catalyst surface Fe ions redox cycle, also make catalyst lose activity.Which is understood fully
, on catalyst performance with significantly affecting, the industrialization to butadiene catalyst made by butylene oxidation dehydrogen should for micro or oligo-element
With obviously significant.During the course of the reaction, the addition of appropriate vapor can reduce the partial pressure of reactant butylene, stable
Reaction temperature, and suppress and eliminate catalyst surface formation carbon distribution, butadiene selective is improved, to maintaining catalyst stability
Also there is important function.The method for preparing catalyst is easy, high with butadiene selective, and accessory substance is particularly deep oxidation
Thing is less, the high advantage of catalyst performance stabilised, improves the resource utilization of butylene oxidation-dehydrogenation process, reduces carbon
Discharge.
Butylene oxidation-dehydrogenation reaction is carried out on the miniature catalyst reaction device of continuous flowing quartz tube reactor.Product analysis are adopted
HP-5890 gas chromatographs (HP-AL/S capillary columns, 50m × 0.53mm × 15 μm；Fid detector) on-line analysis take off
The content of alkane, alkene, butadiene in hydrogen product etc. simultaneously calculates the conversion ratio and selectivity of product of reaction.Using this
Catalyst prepared by the method for bright offer reaches 75～82% for butylene oxidation-dehydrogenation reaction, butane total conversion, butadiene
Selectively up to 95%, oxygen-containing accessory substance is less.Catalyst performance is preferable and stability is high, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
Weigh appropriate highly purified ferric nitrate and magnesium nitrate is mixed in 1L deionized waters, stir.Then will be above-mentioned molten
Liquid is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by gained solid in an oven 110
DEG C drying 4 hours.Again roasting obtains catalyst A for 4 hours to dried sample at 600 DEG C in Muffle furnace, grinding
It is used for evaluating catalyst into 40～60 mesh particles.The component containing Fe of catalyst A consists of Fe2O3·2MgFe2O4, catalysis
In agent in terms of mass fraction also 100ppm containing Cs, Al 50ppm, P 100ppm.
【Embodiment 2】
Weigh appropriate highly purified ferric nitrate and magnesium nitrate is mixed in 1L deionized waters, stir.Then will be above-mentioned molten
Liquid is co-precipitated with 10% ammonia spirit, and precipitation pH value is maintained at 6.0, and precipitation temperature is 10 DEG C, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by 90 DEG C in an oven of gained solid
It is dried 24 hours.Again roasting obtains catalyst B for 24 hours to dried sample at 400 DEG C in Muffle furnace, grinding
It is used for evaluating catalyst into 40～60 mesh particles.The component containing Fe of catalyst B consists of Fe2O3·20MgFe2O4, catalysis
In agent in terms of mass fraction also 100ppm containing Cs, Al 200ppm, P 300ppm.
【Embodiment 3】
During appropriate highly purified ferric nitrate and magnesium nitrate are weighed together in 1L deionized waters, stir.Then by above-mentioned solution
It is co-precipitated with 30% ammonia spirit, precipitation pH value is maintained at 12, and precipitation temperature is 80 DEG C, then uses centrifugation
Machine separates the solid sample in precipitated product, is washed with 4L deionized waters, by 150 DEG C in an oven of gained solid
It is dried 1 hour.Again roasting obtains catalyst C in 1 hour to dried sample at 650 DEG C in Muffle furnace, grinds to form
40～60 mesh particles are used for evaluating catalyst.The component containing Fe of catalyst C consists of 20Fe2O3·1MgFe2O4, catalysis
In agent in terms of mass fraction also 300ppm containing Cs, Al 200ppm, P 100ppm.
【Embodiment 4】
Weigh appropriate highly purified ferric nitrate and magnesium nitrate is mixed in 1L deionized waters, stir.Then by catalyst
Precursor solution is co-precipitated with 15% ammonia spirit, and precipitation pH value is maintained at 8.0, and precipitation temperature is 40 DEG C, Ran Houyong
Centrifugal separator separates the solid sample in precipitated product, is washed with 4L deionized waters, by gained solid in baking oven
In 110 DEG C of dryings 4 hours.Again roasting obtains catalyst D in 4 hours to dried sample at 600 DEG C in Muffle furnace,
40～60 mesh particles are ground to form for evaluating catalyst.The component containing Fe of catalyst D consists of 1Fe2O3·5MgFe2O4,
In catalyst in terms of mass fraction also 200ppm containing Cs, Al 300ppm, P 100ppm.
【Embodiment 5】
Weigh appropriate highly purified ferric nitrate and magnesium nitrate is mixed in 1L deionized waters, stir.Then by catalyst
Precursor solution is co-precipitated with 25% ammonia spirit, and precipitation pH value is maintained at 10.0, and precipitation temperature is 60 DEG C, then
The solid sample in precipitated product is separated with centrifugal separator, is washed with 4L deionized waters, gained solid is being dried
110 DEG C of dryings 4 hours in case.Again roasting obtains catalyst in 4 hours to dried sample at 600 DEG C in Muffle furnace
E, grinds to form 40～60 mesh particles for evaluating catalyst.The component containing Fe of catalyst E consists of 5Fe2O3·1MgFe2O4,
In catalyst in terms of mass fraction also 150ppm containing Cs, Al 75ppm, P 200ppm.
【Embodiment 6】
Weigh appropriate highly purified ferric nitrate and zinc nitrate is mixed in 1L deionized waters, stir.Then will be above-mentioned molten
Liquid is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by gained solid in an oven 110
DEG C drying 4 hours.Again roasting obtains catalyst F for 4 hours to dried sample at 600 DEG C in Muffle furnace, grinding
It is used for evaluating catalyst into 40～60 mesh particles.The component containing Fe of catalyst F consists of 1Fe2O3·2ZnFe2O4, catalysis
In agent in terms of mass fraction also 200ppm containing Cs, Al 200ppm, P 200ppm.
【Embodiment 7】
Weigh appropriate highly purified ferric nitrate, magnesium nitrate, zinc nitrate and antimony oxide to be mixed in 1L deionized waters, stirring is equal
It is even.Then above-mentioned solution is co-precipitated with 20% ammonia spirit, precipitation pH value is maintained at 9.5, and precipitation temperature is room
Temperature, is then separated the solid sample in precipitated product with centrifugal separator, is washed with 4L deionized waters, by gained
Solid 110 DEG C of dryings 4 hours in an oven.Again roasting is obtained dried sample for 4 hours at 600 DEG C in Muffle furnace
To catalyst G, 40～60 mesh particles are ground to form for evaluating catalyst.The component containing Fe of catalyst G is consisted of
1Fe2O3·2MgFe2O4·2ZnFe2O4, also containing Os 0.05%, Cs 100ppm, Al in terms of mass fraction in catalyst
100ppm、P 100ppm。
【Embodiment 8】
Weigh appropriate highly purified ferric nitrate, magnesium nitrate, manganese nitrate and antimony oxide to be mixed in 1L deionized waters, stirring is equal
It is even.Then above-mentioned solution is co-precipitated with 20% ammonia spirit, precipitation pH value is maintained at 9.5, and precipitation temperature is room
Temperature, is then separated the solid sample in precipitated product with centrifugal separator, is washed with 4L deionized waters, by gained
Solid 110 DEG C of dryings 4 hours in an oven.Again roasting is obtained dried sample for 4 hours at 600 DEG C in Muffle furnace
To catalyst H, 40～60 mesh particles are ground to form for evaluating catalyst.The component containing Fe of catalyst H is consisted of
1Fe2O3·2MgFe2O4·2MnFe2O4, in catalyst in terms of mass fraction also containing Os 10%, Cs 300ppm, Al 300ppm,
P 300ppm。
【Embodiment 9】
Weigh appropriate highly purified ferric nitrate, magnesium nitrate, zinc nitrate, nickel nitrate and antimony oxide to be mixed in 1L deionized waters,
Stir.Then above-mentioned solution is co-precipitated with 20% ammonia spirit, precipitation pH value is maintained at 9.5, precipitation temperature
Spend for room temperature, then separated the solid sample in precipitated product with centrifugal separator, washed with 4L deionized waters,
By gained solid 110 DEG C of dryings 4 hours in an oven.The roasting 4 at 600 DEG C in Muffle furnace again of dried sample
Hour obtains catalyst I, grinds to form 40～60 mesh particles for evaluating catalyst.The component containing Fe of catalyst I is consisted of
1Fe2O3·2MgFe2O4·2ZnFe2O4·1NiFe2O4, in catalyst in terms of mass fraction also containing Os 2%, Cs 350ppm,
Al 100ppm、P 50ppm。
【Embodiment 10】
The ferric nitrate and magnesium nitrate for weighing appropriate higher degree is mixed in 1L deionized waters, is stirred.Then will be above-mentioned
Solution is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by 110 DEG C in an oven of gained solid
It is dried 4 hours.Again roasting obtains catalyst J in 4 hours to dried sample at 600 DEG C in Muffle furnace, grind to form 40～
60 mesh particles are used for evaluating catalyst.The component containing Fe of catalyst J consists of Fe2O3·2MgFe2O4, with matter in catalyst
Amount fraction meter also 550ppm containing Cs, Al 450ppm, P 550ppm.
【Embodiment 11】
The ferric nitrate and magnesium nitrate for weighing appropriate higher degree is mixed in 1L deionized waters, is stirred.Then will be above-mentioned
Solution is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by 110 DEG C in an oven of gained solid
It is dried 4 hours.Again roasting obtains catalyst K in 4 hours to dried sample at 600 DEG C in Muffle furnace, grinds to form
40～60 mesh particles are used for evaluating catalyst.The component containing Fe of catalyst K consists of Fe2O3·2MgFe2O4, in catalyst
Also 650ppm containing Cs, Al 650ppm, P 750ppm in terms of mass fraction.
【Embodiment 12】
The ferric nitrate and magnesium nitrate for weighing appropriate higher degree is mixed in 1L deionized waters, is stirred.Then will be above-mentioned
Solution is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by 110 DEG C in an oven of gained solid
It is dried 4 hours.Again roasting obtains catalyst L in 4 hours to dried sample at 600 DEG C in Muffle furnace, grind to form 40～
60 mesh particles are used for evaluating catalyst.The component containing Fe of catalyst L consists of Fe2O3·2MgFe2O4, with matter in catalyst
Amount fraction meter also 850ppm containing Cs, Al 820ppm, P 890ppm.
【Embodiment 13】
The ferric nitrate and magnesium nitrate for weighing appropriate higher degree is mixed in 1L deionized waters, is stirred.Then will be above-mentioned
Solution is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by 110 DEG C in an oven of gained solid
It is dried 4 hours.Again roasting obtains catalyst M in 4 hours to dried sample at 600 DEG C in Muffle furnace, grinds to form
40～60 mesh particles are used for evaluating catalyst.The component containing Fe of catalyst M consists of Fe2O3·2MgFe2O4, in catalyst
Also 200ppm containing Cs, Al 200ppm, P 850ppm in terms of mass fraction.
【Embodiment 14】
The ferric nitrate and magnesium nitrate for weighing appropriate higher degree is mixed in 1L deionized waters, is stirred.Then will be above-mentioned
Solution is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by 110 DEG C in an oven of gained solid
It is dried 4 hours.Again roasting obtains catalyst n in 4 hours to dried sample at 600 DEG C in Muffle furnace, grinds to form
40～60 mesh particles are used for evaluating catalyst.The component containing Fe of catalyst n consists of Fe2O3·2MgFe2O4, in catalyst
Also 200ppm containing Cs, Al 850ppm, P 450ppm in terms of mass fraction.
【Comparative example 1】
Weighing is mixed in 1L deionized waters in right amount compared with the ferric nitrate and magnesium nitrate of low-purity, is stirred.Then will be above-mentioned
Solution is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by 110 DEG C in an oven of gained solid
It is dried 4 hours.Again roasting obtains catalyst O in 4 hours to dried sample at 600 DEG C in Muffle furnace, grinds to form
40～60 mesh particles are used for evaluating catalyst.The component containing Fe of catalyst O consists of Fe2O3·2MgFe2O4, in catalyst
Also 1000ppm containing Cs, Al 1200ppm, P 1000ppm in terms of mass fraction.
【Comparative example 2】
Weigh ferric nitrate appropriate compared with low-purity, magnesium nitrate, manganese nitrate and antimony oxide to be mixed in 1L deionized waters, stir
Uniformly.Then above-mentioned solution is co-precipitated with 20% ammonia spirit, precipitation pH value is maintained at 9.5, and precipitation temperature is
Room temperature, is then separated the solid sample in precipitated product with centrifugal separator, is washed with 4L deionized waters, by institute
Solid 110 DEG C of dryings 4 hours in an oven.Dried sample again in Muffle furnace at 600 DEG C roasting 4 hours
Catalyst P is obtained, 40～60 mesh particles is ground to form for evaluating catalyst.The component containing Fe of catalyst P is consisted of
1Fe2O3·2MgFe2O4·2MnFe2O4, also containing Os 10%, Cs 2000ppm, Al in terms of mass fraction in catalyst
200ppm、P 100ppm。
【Comparative example 3】
Weighing is mixed in 1L deionized waters in right amount compared with the ferric nitrate and magnesium nitrate of low-purity, is stirred.Then will be above-mentioned
Solution is co-precipitated with 20% ammonia spirit, and precipitation pH value is maintained at 9.5, and precipitation temperature is room temperature, then with centrifugation point
Disembark and separate the solid sample in precipitated product, washed with 4L deionized waters, by 110 DEG C in an oven of gained solid
It is dried 4 hours.Again roasting obtains catalyst Q in 4 hours to dried sample at 600 DEG C in Muffle furnace, grinds to form
40～60 mesh particles are used for evaluating catalyst.The component containing Fe of catalyst Q consists of Fe2O3·2MgFe2O4, in catalyst
Also 100ppm containing Cs, Al 1500ppm, P 1200ppm in terms of mass fraction.
【Embodiment 15】
Taking 0.5g catalyst A～Q carries out butylene oxidation-dehydrogenation evaluation.Feeding gas be butylene, oxygen, the mixture of vapor,
Wherein butylene：Oxygen：The constitutive molar ratio of water is 1：0.75：10, first unstrpped gas is sufficiently mixed, it is re-introduced into
Oxidative dehydrogenation is carried out in reactor.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；Butylene quality is empty
Speed is 5h-1.Catalytic reaction is carried out under above-mentioned condition, product is analyzed with gas chromatography.Reaction result is listed in table
1。
Table 1*
* butene conversion and the butadiene selective of 10 hours are reacted
【Embodiment 16】
Taking 0.5g catalyst A, P carries out butylene oxidation-dehydrogenation evaluation.Feeding gas be butylene, oxygen, the mixture of vapor,
Wherein butylene：Oxygen：The constitutive molar ratio of water is 1：0.75：10, first unstrpped gas is sufficiently mixed, it is re-introduced into
Oxidative dehydrogenation is carried out in reactor.Reactor inlet temperatures are 340 DEG C；Reaction pressure is normal pressure；Butylene quality is empty
Speed is 5h-1.Catalytic reaction is carried out under above-mentioned condition, product is analyzed with gas chromatography.Reaction result is listed in table
2。
Table 2
Claims (10)
1. a kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene, includes Fe in component3+, it is characterised in that catalyst
The mass content of middle Cs elements is less than 900ppm；The mass content of Al elements is less than 900ppm.
2. the catalyst of Oxidative Dehydrogenation of Butene into Butadiene is used for according to claim 1, it is characterised in that the Cs is first
The mass content of element is less than 800ppm；The mass content of Al elements is less than 800ppm.
3. the catalyst of Oxidative Dehydrogenation of Butene into Butadiene is used for according to claim 2, it is characterised in that the Cs is first
The mass content of element is less than 600ppm；The mass content of Al elements is less than 600ppm.
4. the catalyst of Oxidative Dehydrogenation of Butene into Butadiene is used for according to claim 3, it is characterised in that the Cs is first
The mass content of element is less than 400ppm；The mass content of Al elements is less than 400ppm.
5. the catalyst of Oxidative Dehydrogenation of Butene into Butadiene is used for according to claim 1, it is characterised in that P in catalyst
The mass content of element is less than 900ppm.
6. the catalyst of Oxidative Dehydrogenation of Butene into Butadiene is used for according to claim 5, it is characterised in that P in catalyst
The mass content of element is less than 400ppm.
7. the catalyst of Oxidative Dehydrogenation of Butene into Butadiene is used for according to claim 1, it is characterised in that catalyst
Fe3+For α-Fe2O3Or Fe2O4 2-In at least one.
8. the catalyst of Oxidative Dehydrogenation of Butene into Butadiene is used for according to claim 1, it is characterised in that catalyst is also
Comprising Os elements, the mass content of Os elements is 0.05～10% in catalyst.
9. a kind of application of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene, with butylene, oxygen-containing gas, vapor
Gaseous mixture 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 right
Require to obtain butadiene after the catalyst haptoreaction described in 1～8 any one.
10. the application of the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, butylene in reactant are used for according to claim 9：
Oxygen：The volume ratio of vapor is 1：(0.5～5)：(2～20).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072110A (en) * | 1991-11-01 | 1993-05-19 | 中国科学院兰州化学物理研究所 | Butylene oxidation dehydrogenation catalyst for fluidized bed |
| CN1169685A (en) * | 1994-12-14 | 1998-01-07 | 国际壳牌研究有限公司 | Recombined iron dioxide |
| CN103657680A (en) * | 2012-09-26 | 2014-03-26 | 上海华谊丙烯酸有限公司 | Ferrate catalyst, preparation method and application of ferrate catalyst |
-
2015
- 2015-10-22 CN CN201510689789.0A patent/CN106607064A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072110A (en) * | 1991-11-01 | 1993-05-19 | 中国科学院兰州化学物理研究所 | Butylene oxidation dehydrogenation catalyst for fluidized bed |
| CN1169685A (en) * | 1994-12-14 | 1998-01-07 | 国际壳牌研究有限公司 | Recombined iron dioxide |
| CN103657680A (en) * | 2012-09-26 | 2014-03-26 | 上海华谊丙烯酸有限公司 | Ferrate catalyst, preparation method and application of ferrate catalyst |
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Application publication date: 20170503 |