CN109833903A - A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparation and application - Google Patents
A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparation and application Download PDFInfo
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Abstract
A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst.The catalyst activity component is one or more of chromium, molybdenum, tungsten, vanadium, iron, cobalt, nickel, zinc, gallium, carrier is that zeolite molecular sieve or SAPO Series Molecules sieve, auxiliary agent is one or more of boron, phosphorus, sulphur, silica and halogen, active component weight percentage is 0.5~5%, and auxiliary element is 0.1~5%.Preparation process step are as follows: 1) be dried molecular sieve carrier；2) it is impregnated with the solution containing active component, dry, roasting；3) it is impregnated with the solution containing auxiliary element, dry, roasting.This catalyst has preferable stability, conversion ratio and product yield to low-carbon alkanes reaction.
Description
Technical field
The present invention relates to a kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparations and application.
Background technique
Low-carbon alkene is important industrial chemicals, and demand constantly increases in recent years, and notch is larger.Existing low-carbon alkene
In production method, using conventional petroleum as the production path of the catalytic cracking of raw material and naphtha steam cracking at high price, source
In natural gas, associated gas, shale gas, petrochemical industry and oil refining process by-product low-carbon alkanes, rich reserves are cheap, but because
The inertia of C-H bond, utilization rate are lower always.Preparing low-carbon alkene as raw material direct dehydrogenation using low-carbon alkanes helps to optimize
Carbon resource utilizes, also because its price advantage is receive more and more attention.Manufacturing olefin by low-carbon alkane dehydrogenation under oxidizing atmosphere
Technology can overcome thermodynamics to the limitation of conversion ratio, help to obtain higher product yield under the conditions of relative low temperature, but
It is limited to the safety factor of practical operation and the limitation of existing catalyst research and development, still can not achieve industrial production.
The researchs such as J.S.Valente find that the MoVTeNb of current oxidative dehydrogenation of ethane excellent effect at 500 DEG C or more, catalyst
Structure, which changes, leads to activity reduction (J.S.Valente, et al., ACS Catal.2014,4,1292-1301), right
In the oxidative dehydrogenation system for being also easy to produce hot spot, it is larger lower than 500 DEG C of difficulty to control reaction bed temperature.In comparison, nothing
Low-carbon alkanes catalytic dehydrogenation alkene operability is stronger under oxygen system.Although low-carbon alkanes catalytic dehydrogenation system under current anaerobic system
Alkene has realized industrialization, but existing industrial catalyst mostly uses expensive noble metal platinum or the disagreeableness chrome catalysts of environment,
And catalyst inactivation is very fast, affects product yield, catalyst be also required to carry out frequent cycle regeneration (J.J.H.B.Sattler,
et al.,Chem.Rev.2014,114,10613-10653).In this regard, numerous studies have also been made in many scholars.For example,
V.Galvita etc. has studied catalytic effect of PtSn/Mg (Al) the O catalyst in the reaction of ethane anaerobic dehydrogenation, they have found
In the initial 40min reaction time, catalyst inactivates (V.Galvita, et al., Journal ofCatalysis quickly
2010,271,209–219)。
In addition, low-carbon alkanes catalytic dehydrogenation olefine reaction olefine selective is higher compared with conventional olefin production ways,
It is again inadequate to make aromatics production, and dry gas is more in aromatizing low-carbon paraffin reaction product, easily causes the waste of carbon resource.The U.S.
Patent US8692043B2 reports catalyst system the answering in ethane aromatisation for making auxiliary agent using Pt as dehydrogenation activity center and Fe
With methane selectively is 24% or more as the result is shown.The researchs such as V.I.Zaikovskii find what Pt, Pd were modified
Galloaluminosilicate catalyst is in ethane aromatization, and the selectivity of methane production is 18% or more
(V.I.Zaikovskii,et al.,KINETICS AND CATALYSIS,2012,53,731–736).Therefore, low-carbon is developed
Alkane anaerobic dehydrogenation alkene and by-product aromatic hydrocarbons simultaneously there is the catalyst of lower methane selectively to be of great significance.
Summary of the invention
Present invention is generally directed to existing catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, especially ethane dehydrogenation catalyst stability
Problem poor, feed stock conversion is lower, product yield is lower, it is de- that the present invention provides a kind of low-carbon alkanes (C2~C6) anaerobics
Hydrogen alkene catalyst and its preparation and application.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst active component is chromium, molybdenum, tungsten, vanadium, iron, cobalt, nickel, zinc, gallium
One or more of, preferably molybdenum；Carrier is that zeolite molecular sieve or SAPO Series Molecules sieve；Auxiliary agent
For boron, phosphorus, sulphur, halogen and with the one or more of silica, preferably phosphorus；Wherein, active group
Dividing mass percentage is 0.5~5%, and auxiliary element is 0.1~5%.
The carrier is the molecular sieve containing ten-ring structure.
The molecular sieve containing ten-ring structure is ZSM5 or MCM22, wherein silica alumina ratio (SiO2/Al2O3)
It is 30~200.
The preparation method of low-carbon alkanes anaerobic dehydrogenation alkene catalyst, comprising the following steps:
1) by molecular sieve in 60~120 DEG C of vacuum drying treatments 1~for 24 hours；
2) solution containing catalyst activity component is added dropwise to dropwise and the molecule of processing is pre-dried is sieved to thorough impregnation；
3) catalyst for obtaining 2) step stand 1 at 15~35 DEG C~for 24 hours after dry 12h at 110 DEG C；
4) 1~12h of Muffle kiln roasting by the catalyst 3) obtained at 400~650 DEG C；
5) catalyst for making 4) preparation is added dropwise up to thorough impregnation in the solution containing auxiliary element；
6) catalyst for obtaining 5) step stand 1 at 15~35 DEG C~for 24 hours after dry 12h at 110 DEG C；
7) it is de- to obtain low-carbon alkanes anaerobic by Muffle 1~12h of kiln roasting by the catalyst 6) obtained at 400~650 DEG C
Hydrogen alkene catalyst.
The activity component impregnation liquid that the catalyst preparation process uses is the nitrate of active component, oxysalt or oxygen
One or more of ammonia spirit of compound.
The adjuvant component maceration extract that the catalyst preparation process uses is one of respective acids, acid compound or ammonium salt
Or it is two or more.
The adjuvant component maceration extract is preferably solution containing phosphate, and solution containing phosphate is phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate or phosphorus
One or more of acid dihydride ammonia.
The catalyst is reacted for low-carbon alkanes (C2~C6) anaerobic dehydrogenation, reaction condition are as follows: and 450~650 DEG C, air speed
2500~7000ml/gcat/ h, reaction pressure are 0.01Mpa~normal pressure, gas composition gas composition: 10%~100%C2H6, adopt
With fixed bed or fluidized-bed reactor.
Compared with the prior art, the advantages of the present invention are as follows:
The conversion ratio that low-carbon alkanes are improved using acidic molecular sieve as carrier inhibits catalyst by the introducing of the auxiliary agents such as phosphorus
Rapid deactivation improves catalyst stability and ethylene selectivity, while by-product aromatic hydrocarbons.
Detailed description of the invention
Fig. 1 is the catalyst performance figure of 1 catalyst A of embodiment.
Fig. 2 is the catalyst performance figure of 2 catalyst B of embodiment.
Fig. 3 is the catalyst performance figure of 1 catalyst C of comparative example.
Specific embodiment
Technology of the invention is further described below by way of example.
Embodiment 1
Catalyst A: catalyst activity component is molybdenum；Carrier is HZSM5；Auxiliary agent is phosphorus；Wherein, active group sub-prime
Measuring percentage composition is 5%, and auxiliary agent mass percentage is 2.5%.
It is supported on HZSM5 for 5wt%Mo and 2.5wt%P, the preparation method is as follows:
1) HZSM5 dry powder is dried in vacuo 12h at 120 DEG C；
2) NH that impregnation increment is equivalent to 5wt%Mo is prepared4Mo7O24.4H2O solution, by NH4Mo7O24.4H2O solution is equably
It is added drop-wise on carrier, stirring makes dipping uniformly, stands 12h at room temperature, 12h is dried at 110 DEG C, in Muffle furnace in air atmosphere
500 DEG C of roasting 6h.Solution quality: carrier quality 1.5:1.
3) preparation of 5%Mo-2.5%P-HZSM5
Prepare the NH for being equivalent to 2.5wt%P4H2PO4Solution, by NH4H2PO4Solution is equably added drop-wise to 5%Mo-HZSM5
On, stirring makes dipping uniformly, stands 12h at room temperature, 12h, 600 DEG C of roasting 3h in Muffle furnace air atmosphere are dried at 110 DEG C.It is molten
Liquid quality: 5%Mo-HZSM5 mass is 1.5:1.
The catalytic performance of catalyst A is as shown in Figure 1.
Catalyst A is used for the reaction of low-carbon alkanes (C2~C6) anaerobic dehydrogenation,
600 DEG C of reaction temperature, normal pressure, gas composition contains 10%C2H6, air speed 5000ml/gcat/ h, using fixed bed, ethane
For conversion ratio up to 23%, ethylene and arenes selectivity adduction can reach 85%.
Embodiment 2
Catalyst B is that 5wt%Mo and 3wt%P is supported on HZSM5, and preparation step is the same as catalyst A.
The catalyst performance of catalyst B is as shown in Figure 2.
Catalyst B is used for the reaction of low-carbon alkanes (C2~C6) anaerobic dehydrogenation,
600 DEG C of reaction temperature, normal pressure, gas composition contains 10%C2H6, air speed 5000ml/gcat/ h, using fixed bed, ethane
For conversion ratio up to 23%, ethylene and arenes selectivity adduction can reach 85%.
Comparative example 1
Catalyst C is 5wt%Mo-HZSM5 but does not load P, and preparation step is the same as catalyst A
The following Fig. 3 of the catalyst performance of catalyst C
600 DEG C of reaction temperature, normal pressure, gas composition contains 10%C2H6, air speed 5000ml/gcat/h。
Using fixed bed, for ethane conversion up to 24%, ethylene and arenes selectivity adduction can reach 67%.
Embodiment 3
Preparation step is the same as embodiment 1.For catalyst using MCM22 as carrier, 5wt% molybdenum is activated centre, and 2.5wt%P is to help
Agent, catalyst are applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, gas composition contains 10%C2H6,
Air speed 5000ml/gcat/h.For ethane conversion up to 21%, ethylene and arenes selectivity adduction can reach 82%.
Embodiment 4
Preparation step is the same as embodiment 1.Catalyst is with ZSM5 ((SiO2/Al2O3It=50) is carrier, 5wt% gallium is in activity
The heart, 2wt%P are auxiliary agent, and catalyst is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, and gas group
At containing 10%C2H6, air speed 5000ml/gcat/h.Up to 23%, ethylene can reach ethane conversion with arenes selectivity adduction
75%.
Embodiment 5
Preparation step is the same as embodiment 1.Catalyst is with ZSM5 ((SiO2/Al2O3It=30) is carrier, 5wt% molybdenum is in activity
The heart, 2wt%P are auxiliary agent, and catalyst is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, and gas group
At containing 10%C2H6, air speed 5000ml/gcat/h.Up to 30%, ethylene can reach ethane conversion with arenes selectivity adduction
70%.
Embodiment 6
Preparation step is the same as embodiment 1.With ZSM5 ((SiO2/Al2O3It=50) is carrier, 5wt% molybdenum is activated centre,
1wt% silica is that the catalyst system of auxiliary agent is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, often
Pressure, gas composition contain 10%C2H6, air speed 5000ml/gcat/h.Up to 55%, ethylene and arenes selectivity sum it up ethane conversion
It can reach 77%.
Embodiment 7
Preparation step is the same as embodiment 1.With ZSM5 ((SiO2/Al2O3It=50) is carrier, 5wt% molybdenum is activated centre,
1wt% boron is that the catalyst system of auxiliary agent is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, and gas
Body composition contains 10%C2H6, air speed 5000ml/gcat/h.Up to 55%, ethylene sums it up reachable ethane conversion with arenes selectivity
To 72%.
Embodiment 8
Preparation step is the same as embodiment 1.Using MCM22 as carrier, 5wt% molybdenum is activated centre, and 2wt% silica is auxiliary agent
Catalyst system be applied to ethane anaerobic dehydrogenation reaction in, reaction condition are as follows: 600 DEG C, normal pressure, gas composition contain 10%
C2H6, air speed 5000ml/gcat/h.For ethane conversion up to 50%, ethylene and arenes selectivity adduction can reach 71%.
Embodiment 9
Preparation step is the same as embodiment 1.With ZSM5 ((SiO2/Al2O3It=200) is carrier, 5wt% molybdenum is activated centre,
1wt% phosphorus is that the catalyst system of auxiliary agent is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, and gas
Body composition contains 10%C2H6, air speed 5000ml/gcat/h.Up to 20%, ethylene sums it up reachable ethane conversion with arenes selectivity
To 71%.
Embodiment 10
Preparation step is the same as embodiment 1.Using MCM22 as carrier, 5wt% molybdenum is activated centre, and 0.5wt% chlorine is urging for auxiliary agent
Agent system is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, gas composition contains 10%C2H6, empty
Fast 5000ml/gcat/h.For ethane conversion up to 23%, ethylene and arenes selectivity adduction can reach 68%.
Embodiment 11
Preparation step is the same as embodiment 1.Using MCM22 as carrier, 5wt% gallium is activated centre, and 3wt% phosphorus is the catalysis of auxiliary agent
Agent system is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, gas composition contains 10%C2H6, air speed
5000ml/gcat/h.For ethane conversion up to 23%, ethylene and arenes selectivity adduction can reach 72%.
Embodiment 12
Preparation step is the same as embodiment 1.Using MCM22 as carrier, 5wt% gallium is activated centre, and 1.5wt% silica is to help
The catalyst system of agent is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, gas composition contains 10%
C2H6, air speed 5000ml/gcat/h.For ethane conversion up to 50%, ethylene and arenes selectivity adduction can reach 74%.
Embodiment 13
Preparation step is the same as embodiment 1.With ZSM5 ((SiO2/Al2O3It=50) is carrier, 5wt% gallium is activated centre,
2wt% boron is that the catalyst system of auxiliary agent is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, and gas
Body composition contains 10%C2H6, air speed 5000ml/gcat/h.Up to 23%, ethylene sums it up reachable ethane conversion with arenes selectivity
To 71%.
Embodiment 14
Preparation step is the same as embodiment 1.With ZSM5 ((SiO2/Al2O3It=50) is carrier, 4wt% zinc is activated centre,
1.5wt% phosphorus is that the catalyst system of auxiliary agent is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure,
Gas composition contains 10%C2H6, air speed 5000ml/gcat/h.For ethane conversion up to 24%, ethylene and arenes selectivity adduction can
Reach 73%.
Embodiment 15
Preparation step is the same as embodiment 1.With ZSM5 ((SiO2/Al2O3It=50) is carrier, 3wt% zinc is activated centre,
1wt% chlorine is that the catalyst system of auxiliary agent is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, and gas
Body composition contains 10%C2H6, air speed 5000ml/gcat/h.Up to 30%, ethylene sums it up reachable ethane conversion with arenes selectivity
To 70%.
Embodiment 16
Preparation step is the same as embodiment 1.Using MCM22 as carrier, 3.5wt% chromium is activated centre, and 1wt% boron is urging for auxiliary agent
Agent system is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, gas composition contains 10%C2H6, empty
Fast 5000ml/gcat/h.For ethane conversion up to 22%, ethylene and arenes selectivity adduction can reach 72%.
Embodiment 17
Preparation step is the same as embodiment 1.Using MCM22 as carrier, 4wt% cobalt or iron or nickel are activated centre, and 5wt% sulphur is to help
The catalyst system of agent is applied in the reaction of ethane anaerobic dehydrogenation, reaction condition are as follows: 600 DEG C, normal pressure, gas composition contains 10%
C2H6, air speed 5000ml/gcat/h.For ethane conversion up to 19%, ethylene and arenes selectivity adduction can reach 69%.
Examples detailed above shows that the catalyst provided using the method for the present invention can effectively improve low-carbon alkanes especially ethane
Conversion ratio and selectivity of light olefin inhibit carbon distribution, improve catalyst stability, and then improve the utilization efficiency of carbon resource.
Although the present invention describes above-mentioned corresponding specific example and catalyst composition, catalyst provided by the invention is simultaneously
It is not limited only to this.
Claims (7)
1. a kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst, it is characterised in that: the catalyst composition is as follows: catalyst is living
Property group is divided into one or more of chromium, molybdenum, tungsten, vanadium, iron, cobalt, nickel, zinc, gallium, preferably molybdenum；Carrier is zeolite molecules
Sieve or SAPO Series Molecules sieve；Auxiliary agent be boron, phosphorus, sulphur, halogen and the one or more with silica, preferably
For phosphorus；Wherein, active component mass percentage is 0.5~5%, and auxiliary element is 0.1~5%.
2. low-carbon alkanes anaerobic dehydrogenation alkene catalyst according to claim 1, it is characterised in that: the carrier be containing
There is the molecular sieve of ten-ring structure.
3. low-carbon alkanes anaerobic dehydrogenation alkene catalyst according to claim 2, it is characterised in that: contain ten-ring knot
The molecular sieve of structure is ZSM5 or MCM22, wherein silica alumina ratio (SiO2/Al2O3) it is 30~200.
4. a kind of preparation method of low-carbon alkanes anaerobic dehydrogenation alkene catalyst described in claim 1, it is characterised in that: packet
Containing following steps:
1) by molecular sieve in 60~120 DEG C of vacuum drying treatments 1~for 24 hours；
2) solution containing catalyst activity component is added dropwise to dropwise and the molecule of processing is pre-dried is sieved to thorough impregnation；
3) catalyst for obtaining 2) step stand 1 at 15~35 DEG C~for 24 hours after dry 12h at 110 DEG C；
4) 1~12h of Muffle kiln roasting by the catalyst 3) obtained at 400~650 DEG C；
5) catalyst for making 4) preparation is added dropwise up to thorough impregnation in the solution containing auxiliary element；
6) catalyst for obtaining 5) step stand 1 at 15~35 DEG C~for 24 hours after dry 12h at 110 DEG C；
7) 6) catalyst obtained is obtained into low-carbon alkanes anaerobic dehydrogenation system in 400~650 DEG C of Muffle 1~12h of kiln roasting
Alkene catalyst.
5. low-carbon alkanes anaerobic dehydrogenation alkene catalyst preparation method according to claim 4, it is characterised in that: catalysis
The activity component impregnation liquid that agent preparation process uses is in the ammonia spirit of the nitrate of active component, oxysalt or oxide
One or more.
6. low-carbon alkanes anaerobic dehydrogenation alkene catalyst preparation method according to claim 4, catalyst preparation process
The adjuvant component maceration extract used is one or more of the respective acids of adjuvant component, acid compound or ammonium salt.
7. a kind of application of low-carbon alkanes anaerobic dehydrogenation alkene catalyst described in claim 1, which is characterized in that catalyst
Applied to low-carbon alkanes anaerobic dehydrogenation olefine reaction, reaction condition are as follows: 450~650 DEG C, 2500~7000ml/gcat/ of air speed
H, reaction pressure is 0.01Mpa~normal pressure, using fixed bed or fluidized-bed reactor.
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