CN105363484B - Catalyst for dehydrogenating low-carbon alkane producing light olefins and its application - Google Patents
Catalyst for dehydrogenating low-carbon alkane producing light olefins and its application Download PDFInfo
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- CN105363484B CN105363484B CN201410428977.3A CN201410428977A CN105363484B CN 105363484 B CN105363484 B CN 105363484B CN 201410428977 A CN201410428977 A CN 201410428977A CN 105363484 B CN105363484 B CN 105363484B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins and its application, mainly solve the problems, such as that the catalyst activity for being currently used for dehydrogenating low-carbon alkane producing light olefins is relatively low, carbon deposit is serious, one way stability is poor.The present invention passes through a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins and its application, the catalyst is using silica-base material as carrier, using platinum group and barium oxide as active component, using IB races element, rare earth element and Group IIIA element oxide as auxiliary agent, it is loaded using the method for dipping, the regenerated technical solution of Burning Coke on Catalyst is finally carried out, this is preferably solved the problems, such as, can be used in the industrial production of dehydrogenating low-carbon alkane producing light olefins.
Description
Technical field
The present invention relates to a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins and its applications.
Background technology
It is gradually insufficient currently, low-carbon alkene raw material is because demand increases, and in natural gas and oil plant obtain it is big
It measures cheap low-carbon alkanes and is mainly used as domestic fuel, be not yet received and make full use of, added value is very low, utilizes dehydrogenating low-carbon alkane
Low-carbon alkene is produced, there is huge application prospect.Low-carbon alkene is a kind of important Organic Chemicals, is widely used in medicine
The production of object, plastics, synthetic rubber, gasoline additive, ion exchange resin, detergent, fragrance and various chemical intermediates.With
The development for chemical industry quickly to the demand growth of low-carbon alkene is developed by the low carbon alkane preparing low-carbon olefins of added value
Process is of great significance for making full use of low-carbon alkanes resource, opening up new alkene source.Propylene/isobutene essentially from
Coproduction or the by-product of the steam cracking and refinery factory fluid catalytic cracking process of naphtha and liquefied petroleum gas only lean on above-mentioned at present
Method has been difficult to meet the needs of China's chemical industry is fast-developing.Propane/dehydrogenation of isobutane technology has become to be split after steam
Important propylene/isobutene source after the coproduction of solution and fluid catalytic cracking process or by-product.
Dehydrogenating low-carbon alkane catalysis reaction carries out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, develops high living
Property, highly selective and high stability catalyst become the technology key.There are two main classes for current industrialized catalyst,
One kind is using metal oxide as active component, as Chinese patent (CN200910012450.1, CN200610126812.6) is disclosed
With the catalyst that chromium is main active component, it is active high, cost is relatively low the advantages that, but inactivate it is fast and toxic, be difficult to
Meet environmental requirement.Another kind of is loaded noble metal catalyst, if the catalyst of United States Patent (USP) (US4438288) report is with Pt
Platinum, tin are carried on γ-Al using infusion process using Sn as auxiliary agent for active component2O3、SiO2Or on the carriers such as MgO, and impregnate
Alkali or alkaline earth metal is added, the shortcomings that catalyst, is that activity and selectivity is relatively low, iso-butane conversion ratio is 39%~
44%.Pt is loaded to MgAl (O) combined oxidation by catalyst disclosed in Chinese patent (CN 96117222.3) using infusion process
Object carrier, the initial iso-butane conversion ratio of the catalyst are 59%, and selective isobutene is 97%~98%, but catalyst inactivation
Comparatively fast, iso-butane conversion ratio is down to 45.6% after reacting 5 hours.Chinese patent (CN200710020064.8) and
(CN200710133324.2) disclose infusion process preparation platinum and tin-rare earth catalyst for dehydrogenating propane react, carrier for containing
X-type, Y types or the ZSM-5 molecular sieve of Na has higher Propylene Selectivity, but conversion of propane is maintained at about 30%, the patent
The stability data of multiple coke-burning regeneration process is not provided.
Catalyst for dehydrogenation of low-carbon paraffin has been achieved with greater advance at present, but that there are still catalytic activity is relatively low, and catalyst holds
The problems such as easy coking deactivation, activity declines after frequent regeneration.The present invention is using silica-base material as carrier, with platinum group and vanadium oxygen
Compound is active component, using IB races element, rare earth element and Group IIIA element oxide as auxiliary agent, it will be apparent that improve catalysis
The dehydrogenation and coking resistivity of agent reduce catalytic dehydrogenation processes cost.
Invention content
The technical problem to be solved by the present invention is to be currently used for the catalyst activity of dehydrogenating low-carbon alkane producing light olefins
Relatively low, carbon deposit is serious, one way stability difference problem, provides a kind of catalysis for dehydrogenating low-carbon alkane producing light olefins newly
Agent, the method for preparing catalyst is easy, and units activity component effective rate of utilization is high, has under the high temperature conditions in use, catalysis
The advantage that agent olefine selective is high, coking deactivation rate is slow, catalyst stability is high.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind being used for dehydrogenating low-carbon alkane system
The catalyst of low-carbon alkene includes following components by weight percentage：
A) using silica-base material as carrier, carrier is the 77~98.78% of catalyst weight；
B) using platinum group and barium oxide as active component, the mass percent that the platinum group accounts for catalyst is
0.1~1.0%, the mass percent that the barium oxide accounts for catalyst is 1~10%；
C) using IB races element as auxiliary agent, IB races element is the 0.01~1.0% of catalyst weight；
D) using the oxide of rare earth element as auxiliary agent, the rare earth oxide be catalyst weight 0.01~
10%；
E) using Group IIIA element oxide as auxiliary agent, the Group IIIA element oxide be catalyst weight 0.1~
1.0%.
In above-mentioned technical proposal, the low-carbon alkanes are propane or iso-butane；Silicon substrate carrier be selected from SBA-15, MCM-41,
One kind in MCM-48 or amorphous silica, carrier are the 77~98.78% of catalyst weight；Platinum group member in active component
The one kind of element in Rh, Pd or Pt, wherein being best with Pt, the weight percent that active component accounts for catalyst is 0.1~
1.0%, content preferred scope is 0.1~0.8%；In active component barium oxide account for catalyst mass percent be 1~
10%, content preferred scope is 2~8%；The one kind of IB races element in Cu, Ag or Au, preferred scope are Cu or Au, wherein
It is best with Au, IB races element is the 0.01~1.0% of catalyst weight, and content preferred scope is 0.05~1.0%；Rare earth oxygen
The one kind of compound auxiliary agent in La, Ce or Nd, preferred scope are one kind in La or Ce, and rare earth oxide auxiliary agent is catalyst
The 0.01~10% of weight, content preferred scope are 0.1~5%；The one kind of Group IIIA element auxiliary agent in Ga or In, IIIA
Race's element oxide is the 0.1~1.0% of catalyst weight, and content preferred scope is 0.1~0.8%.
A kind of preparation method of catalyst for dehydrogenating low-carbon alkane producing light olefins according to the present invention, can be used
Following steps：
1) by solution and the carrier incipient impregnation containing the adjuvant component and vanadium, dipping temperature is 10 DEG C~80
DEG C, dip time is 1~24 hour, is dried, roasts after dipping, and drying temperature is 90 DEG C~150 DEG C, drying time 1
~24 hours, calcination temperature was 400 DEG C~650 DEG C, and roasting time is 1~24 hour；
2) by the solution of the series elements containing Pt and the carrier incipient impregnation, dipping temperature is 10 DEG C~80 DEG C, when dipping
Between be 1~24 hour, be dried, roast after dipping, drying temperature be 90 DEG C~150 DEG C, drying time be 1~24 hour,
Calcination temperature be 400 DEG C~650 DEG C, roasting time be 1~24 hour, then through hydrogen 400 DEG C~650 DEG C reduction treatments 1~
10 hours.
In above-mentioned technical proposal, immersion solvent is using one kind in water or ethyl alcohol.To improve the activity of catalyst, catalyst
After hydrogen reducing, also water vapour can be used to be handled, 400 DEG C~650 DEG C for the treatment of temperature, 1~10 hour time.
Application of the catalyst according to the present invention in manufacturing olefin by low-carbon alkane dehydrogenation can be used and be walked comprising following technique
Suddenly：
1) catalytic dehydrogenation：With low-carbon alkanes and H2Or the gaseous mixture of vapor is raw material, reaction temperature is 400 DEG C~600
DEG C, reaction pressure is 0.08MPa~0.12MPa, and alkane mass space velocity is 3.0~8.0h-1, in the reactor raw material urged with described
Agent carries out catalytic dehydrogenating reaction and obtains low-carbon alkene；
2) catalyst regeneration：Decaying catalyst after reaction carries out coke-burning regeneration, and in-situ regeneration or ex-situ regeneration can be used,
Regeneration temperature is 400 DEG C~650 DEG C, and the recovery time is 1~10 hour, and regeneration atmosphere includes oxygen, air, carbon dioxide or water
At least one of steam.
Compared with prior art, the present invention has the advantages that notable and high-lighting effect, has selected mesoporous silicon material conduct
Carrier, vector stabilisation is high, and catalyst surface has suitable acid-base property；Using platinum group and barium oxide as active component,
Catalyst has higher activity and stability；IB races element is easy to be enriched in catalyst surface, inhibits urge to a certain extent
Agent is to the hydrogenolysis activities of Product olefins, to improve olefin yields；Rare earth oxide and Group IIIA element oxide
Auxiliary agent can play facilitation to the catalysis dehydrogenation performance of catalyst, and suitable auxiliary agent has dispersion, active component is isolated
Effect, it will be apparent that improve the dispersion degree of active component, while also making catalyst that there is better anti-carbon deposition ability.The catalyst
Active advantage higher, olefine selective is high, coking deactivation rate is slow, catalyst stability is high, reduces catalytic dehydrogenation
Process cost.
Dehydrogenating low-carbon alkane reaction carries out on the continuously flowing miniature catalyst reaction device of quartz tube reactor.Product analysis
Using HP-5890 gas chromatographs (HP-AL/S capillary columns, 50m × 0.53mm × 15 μm；Fid detector) on-line analysis is de-
Alkane, olefin(e) centent in hydrogen product and conversion ratio, selectivity and the yield for calculating reaction.Use method provided by the invention
The catalyst of preparation is reacted for dehydrogenating low-carbon alkane, and propane/iso-butane conversion ratio is higher than up to 40%/50%, olefine selective
90%；By 20 coke-burning regenerations, iso-butane conversion ratio is maintained at 50%, and olefine selective is maintained at 90%, catalyst performance
Preferably and stability is high, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific implementation mode
【Embodiment 1】
It weighs 92.1g pure silicon SBA-15 carriers and is added to (the AuCl of gold trichloride containing 0.15g3), 6.23g lanthanum nitrates (La
(NO3)3·6H2O), 1.08g indium nitrates (In (NO3)3) and 6.43g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C
Incipient impregnation 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle
It is roasted 4 hours at 600 DEG C in stove.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pt, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Au is that the load capacity of 0.1%, the La oxides of catalyst weight is the negative of 2%, the In oxides of catalyst weight
Carrying capacity is the 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, 2 are handled at 500 DEG C with vapor
Hour, obtain catalyst A.
【Embodiment 2】
It weighs 92.0g pure silicon SBA-15 carriers and is added to (the AuCl of gold trichloride containing 0.15g3), 6.23g lanthanum nitrates (La
(NO3)3·6H2O), 1.08g indium nitrates (In (NO3)3), 6.43g ammonium metavanadates (NH4VO3) and 0.27g sodium nitrate (NaNO3)
In 60 DEG C of incipient impregnations 2 hours in mixed ethanol solution, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.
Sample after drying roasts 4 hours in Muffle furnace at 600 DEG C again.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of isometric leachings in ethanol solution)
Stain 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying again in Muffle furnace in
It is roasted 4 hours at 600 DEG C, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pt, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Au is that the load capacity of 0.1%, the La oxides of catalyst weight is the negative of 2%, the In oxides of catalyst weight
Carrying capacity is that the load capacity of 0.5%, the Na oxides of catalyst weight is the 0.1% of catalyst weight.In prepared catalyst
Before catalytic dehydrogenating reaction, is handled 2 hours at 500 DEG C with vapor, obtain catalyst B.
【Embodiment 3】
It weighs 98.78g SBA-15 carriers and is added to (the AuCl of gold trichloride containing 0.015g3), 0.031g lanthanum nitrates (La
(NO3)3·6H2O), 0.216g indium nitrates (In (NO3)3), 1.29g ammonium metavanadates (NH4VO3) mixed aqueous solution in 10 DEG C
Incipient impregnation 24 hours, then by 90 DEG C of dryings 24 hours in an oven of the sample after dipping.Sample after drying is again in horse
Not roasted 24 hours at 400 DEG C in stove.
Products obtained therefrom is added to 0.27g chloroplatinic acids (H again2PtCl6.6H2O in 10 DEG C of incipient impregnations in aqueous solution)
24 hours, then by 90 DEG C of dryings 24 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 400
It is roasted 24 hours at DEG C, then through hydrogen reducing 10 hours at 400 DEG C.
The load capacity of Pt is 1%, the Au that 0.1%, the V oxide contents of catalyst weight are catalyst weight in catalyst
Load capacity be catalyst weight 0.01%, La oxides load capacity be catalyst weight 0.01%, In oxides
Load capacity is the 0.1% of catalyst weight.Before prepared catalyst dehydrogenation reaction, with vapor at 400 DEG C
Reason 10 hours, obtains catalyst C.
【Embodiment 4】
It weighs 77g SBA-15 carriers and is added to (the AuCl of gold trichloride containing 1.5g3), 31.15g lanthanum nitrates (La (NO3)3·
6H2O), 2.16g indium nitrates (In (NO3)3) and 12.86g ammonium metavanadates (NH4VO3) mixed aqueous solution in 80 DEG C of isometric leachings
Stain 1 hour, then by 150 DEG C of dryings 1 hour in an oven of the sample after dipping.Sample after drying again in Muffle furnace in
It is roasted 1 hour at 650 DEG C.
Products obtained therefrom is added to 2.73g chloroplatinic acids (H again2PtCl6.6H2O in 80 DEG C of incipient impregnations 1 in aqueous solution)
Hour, then by 150 DEG C of dryings 1 hour in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 650 DEG C
Lower roasting 1 hour, then through hydrogen reducing 1 hour at 650 DEG C.
The load capacity of Pt is 10%, the Au that 1%, the V oxide contents of catalyst weight are catalyst weight in catalyst
Load capacity be catalyst weight 1.0%, La oxides load capacity be catalyst weight 10%, In oxides load
Amount is the 1.0% of catalyst weight.Before prepared catalyst dehydrogenation reaction, it is small that 1 is handled at 650 DEG C with vapor
When, obtain catalyst D.
【Embodiment 5】
It weighs 97.65g SBA-15 carriers and is added to (the AuCl of gold trichloride containing 0.08g3), 0.31g lanthanum nitrates (La
(NO3)3·6H2O), 0.22g indium nitrates (In (NO3)3), 2.58g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C etc.
Volume impregnation 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace
In roasted 4 hours at 600 DEG C.
Products obtained therefrom is added to 0.27g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
The load capacity of Pt is 2%, the Au that 0.1%, the V oxide contents of catalyst weight are catalyst weight in catalyst
Load capacity be catalyst weight 0.05%, La oxides load capacity be catalyst weight 0.1%, In oxides it is negative
Carrying capacity is the 0.1% of catalyst weight.Before prepared catalyst dehydrogenation reaction, 2 are handled at 500 DEG C with vapor
Hour, obtain catalyst E.
【Embodiment 6】
It weighs 84.4g SBA-15 carriers and is added to (the AuCl of gold trichloride containing 1.5g3), 15.58g lanthanum nitrates (La
(NO3)3·6H2O), 1.728g indium nitrates (In (NO3)3) and 10.32g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60
DEG C incipient impregnation 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in horse
Not roasted 4 hours at 600 DEG C in stove.
Products obtained therefrom is added to 2.18g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
The load capacity of Pt is 8%, the Au that 0.8%, the V oxide contents of catalyst weight are catalyst weight in catalyst
Load capacity be catalyst weight 1.0%, La oxides load capacity be catalyst weight 5.0%, In oxides it is negative
Carrying capacity is the 0.8% of catalyst weight.Before prepared catalyst dehydrogenation reaction, 2 are handled at 500 DEG C with vapor
Hour, obtain catalyst F.
【Embodiment 7】
It weighs 92.1g silica MCM-41 carriers and is added to (the CuCl of copper chloride containing 0.21g2), 5.29g cerous nitrates (Ce
(NO3)3·6H2O), 1.36g gallium nitrates (Ga (NO3)3) and 6.43g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C
Incipient impregnation 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle
It is roasted 4 hours at 600 DEG C in stove.
Products obtained therefrom is added to 0.51g palladium bichlorides (PdCl again2) aqueous solution in 60 DEG C of incipient impregnations 2 hours,
Then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying roasts in Muffle furnace at 600 DEG C again
It burns 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pd, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Cu is that the load capacity of 0.1%, the Ce oxides of catalyst weight is the negative of 2%, the Ga oxides of catalyst weight
Carrying capacity is the 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, 2 are handled at 500 DEG C with vapor
Hour, obtain catalyst G.
【Embodiment 8】
It weighs 92.1g pure silicon MCM-48 carriers and is added to (the CuCl of copper chloride containing 0.21g2), 5.29g cerous nitrates (Ce
(NO3)3·6H2O), 1.36g gallium nitrates (Ga (NO3)3) and 6.43g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C
Incipient impregnation 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle
It is roasted 4 hours at 600 DEG C in stove.
Products obtained therefrom is added to 0.60g rhodium chlorides (RhCl again3) aqueous solution in it is small in 60 DEG C of incipient impregnations 2
When, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace at 600 DEG C
Roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Rh, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Cu is that the load capacity of 0.1%, the Ce oxides of catalyst weight is the negative of 2%, the Ga oxides of catalyst weight
Carrying capacity is the 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, 2 are handled at 500 DEG C with vapor
Hour, obtain catalyst H.
【Embodiment 9】
It weighs 92.1g amorphous silica carriers and is added to silver chlorate containing 0.13g (AgCl), 13.03g neodymium nitrates (Nd
(NO3)3·6H2O), 1.36g gallium nitrates (Ga (NO3)3) and 6.43g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C
Incipient impregnation 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle
It is roasted 4 hours at 600 DEG C in stove.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pt, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Ag is that the load capacity of 0.1%, the Nd oxides of catalyst weight is the negative of 2%, the Ga oxides of catalyst weight
Carrying capacity is the 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, 2 are handled at 500 DEG C with vapor
Hour, obtain catalyst I.
【Embodiment 10】
It weighs 92.1g silica MCM-41 carriers and is added to silver chlorate containing 0.13g (AgCl), 13.03g neodymium nitrates (Nd
(NO3)3·6H2O), 1.36g gallium nitrates (Ga (NO3)3) and 6.43g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C
Incipient impregnation 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle
It is roasted 4 hours at 600 DEG C in stove.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pt, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Ag is that the load capacity of 0.1%, the Nd oxides of catalyst weight is the negative of 2%, the Ga oxides of catalyst weight
Carrying capacity is the 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, 2 are handled at 500 DEG C with vapor
Hour, obtain catalyst J.
【Embodiment 11】
It weighs 92.1g pure silicon SBA-15 carriers and is added to silver chlorate containing 0.13g (AgCl), 5.29g cerous nitrates (Ce
(NO3)3·6H2O), 1.08g indium nitrates (In (NO3)3) and 6.43g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C
Incipient impregnation 2 hours, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle
It is roasted 4 hours at 600 DEG C in stove.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pt, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Ag is that the load capacity of 0.1%, the Ce oxides of catalyst weight is the negative of 2%, the In oxides of catalyst weight
Carrying capacity is the 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, 2 are handled at 500 DEG C with vapor
Hour, obtain catalyst K.
【Comparative example 1】
Weigh 98.6g γ-Al2O3Carrier is added to the (SnCl of anhydrous stannic chloride containing 1.04g4) and 1.35g sodium nitrate
(NaNO3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then by the sample after dipping in an oven 110 DEG C it is dry
Dry 4 hours.Sample after drying roasts 4 hours in Muffle furnace at 600 DEG C again.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is catalyst weight that the load capacity of Pt, which is the load capacity of 0.3%, the Sn oxides of catalyst weight, in catalyst
The load capacity of 0.6%, Na oxide is the 0.5% of catalyst weight.Before prepared catalyst dehydrogenation reaction, water is used
Steam is handled 2 hours at 500 DEG C, obtains catalyst L.
【Comparative example 2】
It weighs 92.2g pure silicon SBA-15 carriers and is added to (La (the NO of lanthanum nitrate containing 6.23g3)3·6H2O), 1.36g gallium nitrates
(Ga(NO3)3) and 6.43g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then will leaching
Sample after stain 110 DEG C of dryings 4 hours in an oven.Sample after drying roasts 4 hours in Muffle furnace at 600 DEG C again.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pt, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of La oxides is that the load capacity of 2%, the In oxides of catalyst weight is the 0.5% of catalyst weight.Made
Before standby catalyst dehydrogenation reaction, is handled 2 hours at 500 DEG C with vapor, obtain catalyst M.
【Comparative example 3】
It weighs 94.1g pure silicon SBA-15 carriers and is added to (the AuCl of gold trichloride containing 0.15g3), 1.08g indium nitrates (In
(NO3)3) and 6.43g ammonium metavanadates (NH4VO3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then will be after dipping
Sample 110 DEG C of dryings 4 hours in an oven.Sample after drying roasts 4 hours in Muffle furnace at 600 DEG C again.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pt, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Au is that the load capacity of 0.1%, the In oxides of catalyst weight is the 0.5% of catalyst weight.Prepared
Before catalyst dehydrogenation reaction, is handled 2 hours at 500 DEG C with vapor, obtain catalyst n.
【Comparative example 4】
It weighs 92.6g pure silicon SBA-15 carriers and is added to (the AuCl of gold trichloride containing 0.15g3), 6.23g lanthanum nitrates (La
(NO3)3·6H2) and 6.43g ammonium metavanadates (NH O4VO3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then will
Sample after dipping 110 DEG C of dryings 4 hours in an oven.Roasting 4 is small at 600 DEG C in Muffle furnace again for sample after drying
When.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 5.0% of catalyst weight that the load capacity of Pt, which is 0.3%, the V oxide contents of catalyst weight, in catalyst,
The load capacity of Au is that the load capacity of 0.1%, the La oxides of catalyst weight is the 2% of catalyst weight.It is urged in prepared
Before agent catalytic dehydrogenating reaction, is handled 2 hours at 500 DEG C with vapor, obtain catalyst O.
【Comparative example 5】
It weighs 97.1g pure silicon SBA-15 carriers and is added to (the AuCl of gold trichloride containing 0.15g3), 6.23g lanthanum nitrates (La
(NO3)3·6H2) and 1.08g indium nitrates (In (NO O3)3) mixed aqueous solution in 60 DEG C of incipient impregnations 2 hours, then will
Sample after dipping 110 DEG C of dryings 4 hours in an oven.Roasting 4 is small at 600 DEG C in Muffle furnace again for sample after drying
When.
Products obtained therefrom is added to 0.81g chloroplatinic acids (H again2PtCl6.6H2O in 60 DEG C of incipient impregnations 2 in aqueous solution)
Hour, then by 110 DEG C of dryings 4 hours in an oven of the sample after dipping.Sample after drying is again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, then through hydrogen reducing 2 hours at 500 DEG C.
It is the 0.1% of catalyst weight that the load capacity of Pt, which is the load capacity of 0.3%, Au of catalyst weight, in catalyst,
The load capacity of La oxides is that the load capacity of 2%, the In oxides of catalyst weight is the 0.5% of catalyst weight.Made
Before standby catalyst dehydrogenation reaction, is handled 2 hours at 500 DEG C with vapor, obtain catalyst P.
【Embodiment 12】
It weighs 0.5g catalyst A and carries out dehydrogenating propane evaluation.Feeding gas is propane/H2O=5/3 (vol/vol)；Temperature
550℃；Reaction pressure is normal pressure；Alkane mass space velocity is 4.0h-1Under the conditions of carry out activity rating, test result is listed in table 1.
Table 1*
| Reaction time (h) | Conversion of propane (%) | Propylene Selectivity (%) |
| 6 | 43.6(30.5) | 92.5(82.3) |
| 10 | 43.4(29.7) | 92.3(80.4) |
| 40 | 41.9(27.1) | 91.8(75.1) |
* it is catalyst L data in bracket
【Embodiment 13】
It weighs 0.5g catalyst A~P and carries out dehydrogenation of isobutane evaluation.Feeding gas is iso-butane/H2=5/2 (vol/vol)；
560 DEG C of temperature；Reaction pressure is normal pressure；Alkane mass space velocity is 4.0h-1Under the conditions of carry out activity rating, test result is listed in
Table 2.
Table 2*
| Catalyst | Iso-butane conversion ratio (%) | Selective isobutene (%) |
| A | 53.3 | 91.2 |
| B | 53.2 | 91.1 |
| C | 39.6 | 85.3 |
| D | 57.2 | 84.0 |
| E | 42.7 | 87.4 |
| F | 55.5 | 86.7 |
| G | 52.2 | 91.2 |
| H | 52.0 | 90.5 |
| I | 50.6 | 88.7 |
| J | 50.9 | 88.9 |
| K | 52.6 | 90.3 |
| Comparative example 1 (L) | 34.2 | 81.5 |
| Comparative example 2 (M) | 45.1 | 83.3 |
| Comparative example 3 (N) | 43.5 | 82.4 |
| Comparative example 4 (O) | 45.9 | 81.5 |
| Comparative example 5 (P) | 40.3 | 86.9 |
* 6 hours iso-butane conversion ratios and selective isobutene are reacted
【Embodiment 14】
0.5g catalyst A, 0.5g catalyst L is weighed respectively carries out dehydrogenation of isobutane evaluation.Feeding gas is iso-butane/H2=
5/2(vol/vol)；560 DEG C of temperature；Reaction pressure is normal pressure；Alkane mass space velocity is 4.0h-1Under the conditions of carry out catalytic dehydrogenation work
Property evaluation, after charging 40 hours, regenerated 5 hours under air atmosphere at 560 DEG C, the catalyst after circular response/regeneration 20 times
Reactivity worth is listed in table 3.
Table 3*
* 6 hours iso-butane conversion ratios and selective isobutene are reacted.
Claims (10)
1. a kind of catalyst for dehydrogenating low-carbon alkane producing light olefins includes following components by weight percentage：
A) using silica-base material as carrier, carrier is the 77~98.78% of catalyst weight；
B) using platinum group and barium oxide as active component, the platinum group account for catalyst mass percent be 0.1~
1.0%, the mass percent that the barium oxide accounts for catalyst is 1~10%；
C) using IB races element as auxiliary agent, IB races element is the 0.01~1.0% of catalyst weight；
D) using the oxide of rare earth element as auxiliary agent, the oxide of the rare earth element is the 0.01~10% of catalyst weight；
E) using IIIA races element oxide as auxiliary agent, the oxide of IIIA races element be catalyst weight 0.1~
1.0%。
2. being used for the catalyst of dehydrogenating low-carbon alkane producing light olefins according to claim 1, it is characterised in that the low-carbon
Alkane includes propane and iso-butane.
3. being used for the catalyst of dehydrogenating low-carbon alkane producing light olefins according to claim 1, it is characterised in that the silicon substrate
The one kind of material support in SBA-15, MCM-41, MCM-48 or amorphous silica.
4. being used for the catalyst of dehydrogenating low-carbon alkane producing light olefins according to claim 1, it is characterised in that active component
The one kind of middle platinum group in Rh, Pd or Pt, the weight percent for accounting for catalyst are 0.1~0.8%.
5. being used for the catalyst of dehydrogenating low-carbon alkane producing light olefins according to claim 1, it is characterised in that active component
The mass percent that middle barium oxide accounts for catalyst is 2~8%.
6. being used for the catalyst of dehydrogenating low-carbon alkane producing light olefins according to claim 1, it is characterised in that the IB races
The one kind of element in Cu, Ag or Au, IB races element are the 0.05~1.0% of catalyst weight.
7. being used for the catalyst of dehydrogenating low-carbon alkane producing light olefins according to claim 1, it is characterised in that the rare earth
The one kind of the oxides additive of element in La, Ce or Nd, the oxides additive of rare earth element be catalyst weight 0.1~
5%。
8. being used for the catalyst of dehydrogenating low-carbon alkane producing light olefins according to claim 1, it is characterised in that the IIIA
The one kind of race's element oxide auxiliary agent in Ga or In, the oxide of IIIA races element be catalyst weight 0.1~
0.8%。
9. being used for the catalyst of dehydrogenating low-carbon alkane producing light olefins according to claim 1, it is characterised in that catalyst
Preparation method comprises the steps of：
1) by solution and the carrier incipient impregnation containing the adjuvant component and vanadium, dipping temperature is 10 DEG C~80 DEG C, leaching
The stain time is 1~24 hour, is dried, roasts after dipping, and drying temperature is 90 DEG C~150 DEG C, and drying time is 1~24 small
When, calcination temperature is 400 DEG C~650 DEG C, and roasting time is 1~24 hour；
2) by the solution of the series elements containing Pt and step 1）Products obtained therefrom incipient impregnation, dipping temperature are 10 DEG C~80 DEG C, dipping
Time is 1~24 hour, is dried, roasts after dipping, and drying temperature is 90 DEG C~150 DEG C, and drying time is 1~24 small
When, calcination temperature is 400 DEG C~650 DEG C, and roasting time is 1~24 hour, then through hydrogen in 400 DEG C~650 DEG C reduction treatments 1
~10 hours.
10. a kind of method of dehydrogenating low-carbon alkane producing light olefins, with low-carbon alkanes and H2Or the gaseous mixture of vapor is raw material,
Reaction temperature is 400 DEG C~600 DEG C, and reaction pressure is 0.08MPa~0.12MPa, and alkane mass space velocity is 3.0~8.0h-1, former
Material after claim 1~8 any one of them catalyst haptoreaction with obtaining low-carbon alkene.
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| CN105597766A (en) * | 2016-03-24 | 2016-05-25 | 贺东光 | Catalyst applied to dehydrogenation of light alkane and preparation method thereof |
| CN109289936B (en) * | 2017-07-24 | 2019-11-12 | 中国石油化工股份有限公司 | Spherical mesoporous composite material and preparation method and catalyst and its preparation method and application |
| CN111375415B (en) * | 2018-12-29 | 2022-10-11 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation method thereof |
| CN112473720A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method and application thereof |
| CN113304761B (en) * | 2021-06-11 | 2023-10-20 | 中国科学技术大学 | PtCu 3 Intermetallic compound, preparation method thereof and application of intermetallic compound as dehydrogenation catalyst |
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| EP1916230A1 (en) * | 2006-10-16 | 2008-04-30 | Rohm and Haas Company | Integrated catalytic process for converting alkanes to alkenes and catalysts useful for same |
| CN102000598A (en) * | 2010-10-29 | 2011-04-06 | 广西壮族自治区化工研究院 | Preparation method and application of catalyst for producing olefin by CO2 oxidation and low-carbon alkane dehydrogenation |
| CN102775262A (en) * | 2011-05-13 | 2012-11-14 | 中国石油天然气股份有限公司 | Method for preparation of olefin through light alkane dehydrogenation |
| CN103349988A (en) * | 2013-07-17 | 2013-10-16 | 天津大学 | Platinoid bi-component catalyst as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1916230A1 (en) * | 2006-10-16 | 2008-04-30 | Rohm and Haas Company | Integrated catalytic process for converting alkanes to alkenes and catalysts useful for same |
| CN102000598A (en) * | 2010-10-29 | 2011-04-06 | 广西壮族自治区化工研究院 | Preparation method and application of catalyst for producing olefin by CO2 oxidation and low-carbon alkane dehydrogenation |
| CN102775262A (en) * | 2011-05-13 | 2012-11-14 | 中国石油天然气股份有限公司 | Method for preparation of olefin through light alkane dehydrogenation |
| CN103349988A (en) * | 2013-07-17 | 2013-10-16 | 天津大学 | Platinoid bi-component catalyst as well as preparation method and application thereof |
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