CN106807405B - A kind of preparation method and its catalyst of the catalyst for preparing propylene by dehydrogenating propane - Google Patents
A kind of preparation method and its catalyst of the catalyst for preparing propylene by dehydrogenating propane Download PDFInfo
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- CN106807405B CN106807405B CN201510868382.4A CN201510868382A CN106807405B CN 106807405 B CN106807405 B CN 106807405B CN 201510868382 A CN201510868382 A CN 201510868382A CN 106807405 B CN106807405 B CN 106807405B
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Abstract
The present invention relates to a kind of preparation methods of catalyst for preparing propylene by dehydrogenating propane, using the IVth race's metal element and the bimetallic of group III element metallic combination as auxiliary agent, using platinum family element metal as the active component of catalytic dehydrogenation, using formed alumina as carrier.The preparation process of catalyst includes: that Sn-Al auxiliary agent is introduced alumina support using co-impregnation, spreads more evenly across Sn with atomic level in the carrier, while enhancing the active force between Sn and alumina support；Then dehydrogenation active component is impregnated on the alumina support containing Sn-Al, improves the interaction force between metal-auxiliary agent-carrier；Finally be dried roasting, dechlorination, dipping alkali metal promoter, dipping the post-processings such as dilute hydrochloric acid and vulcanization finally obtain dehydrogenation.The advantages that catalyst of the invention can be used for dehydrogenating low-carbon alkane reaction, and especially dehydrogenating propane reacts, active height, selectivity is good, catalyst stability is good, especially selectivity and stability are obviously improved.
Description
Technical field
Contain Sn, Al bimetallic auxiliary agent, the catalyst for dehydrogenating propane that aluminium oxide is carrier the present invention relates to a kind of
And preparation method thereof, especially improve catalyst for preparing propylene with propane dehydrogenation reactivity, the catalyst system of selectivity and stability
Preparation Method belongs to the catalyst preparation technology of industrial catalysis technical field.
Background technique
Propylene is as important Organic Chemicals, in addition to for that can also be largely used to production third other than producing polypropylene
The chemical products such as alkene is fine, propylene oxide, butanol, octanol, isopropanol, isopropylbenzene, acrylic acid and nonyl phenol.Propylene is mainly derived from
By-products or the coproduction such as naphtha pyrolysis and oil plant FCC technique, account for about the 90% of propylene source.Since the nineties in last century,
As the consumption figure of propylene gradually increases, traditional production of propylene is that raw material is diversified to raw material sources from the simple petroleum that relies on
Technology path transformation, especially low-carbon alkanes be waste alkene technology path.Propane catalytic dehydrogenation prepares propylene
The concern that production technology is increasingly obtained with its highly selective (74-86%), yield have occupied the third position in propylene source, have accounted for about
5%.
Propane catalytic dehydrogenating reaction is limited by thermodynamical equilibrium, and Deposition During Propane Pyrolysis reaction and deep dehydrogenation, selectivity easily occurs
Decline；Catalyst surface carbon deposit is accelerated and rapid deactivation simultaneously.Since lower conversion of propane and catalyst life are short, so that
This method is restricted in industrial application.Therefore exploitation has the dehydrogenating propane system third of high-activity high-selectivity and high stability
The catalyst of alkene becomes the key of the technology.Chinese patent CN200710025372.X discloses mesoporous alumina modified in one
Molecular sieve is the preparation method of platinum-impregnated tin component catalyst on carrier, and conversion of propane is only 17%, propane selectivity 93%.
Chinese patent CN200910011770.5 discloses a kind of auxiliary agent Sn substep and is introduced into alumina support
The propane dehydrogenation catalyst of active component, Sn is uniformly dispersed in the catalyst, and the dehydrogenation activity center ratio of formation is high, catalyst
Selectivity and stability it is high.The dehydrogenating propane that Chinese patent 200910011772.4 discloses a kind of alumina support containing Sn is urged
Sn is introduced carrier in aluminium oxide plastic, carbon nano-fiber is loaded to carrier in situ by cracking of ethylene by agent, the invention
On, activity, selectivity and stability of the catalyst for dehydrogenating propane catalysts greatly improve.Chinese patent
Tin component is introduced Aluminum sol, drying and moulding back loading platinum component and other metals using sol-gal process by 200910057235.3
Auxiliary agent, this process solves Sn component in pyroprocess and is easy reduction precipitation, thus the problem of influencing catalyst performance.China
Patent 201010510192.2 provides a kind of using skeleton bimetallic SBA-15 molecular sieve containing SnAl as the dehydrogenating propane of carrier
The catalyst of propylene processed is formed by binder of inorganic oxide.The catalyst have excellent anti-carbon performance, higher third
Alkane conversion rate of dehydrogenation, selectivity and reaction stability.
The mass ratio of Sn/Pt is higher (2~25) in above-mentioned catalyst, and Sn is easy to happen in high-temperature reaction process and is gone back
Original is precipitated and influences the activity and selectivity of catalyst, causes irreversible inactivation.Sn auxiliary agent is immersed in carrier table by conventional
Face directly interacts weaker with carrier, and being easy to be reduced leads to catalyst inactivation.In addition, the preparation side of above-mentioned carrier
Method is complex, and needs the carrier moulding process in later period.Although dehydrogenating propane conversion ratio and alkene under certain conditions
Selectivity is higher, but due to the easy carbon distribution inactivation of catalyst under hot conditions, causes catalyst reaction stability poor, service life
It is shorter.
Summary of the invention
Aiming at the problems existing in the prior art, the object of the present invention is to provide a kind of urging for preparing propylene by dehydrogenating propane
Agent and preparation method thereof, the present invention can obtain a kind of load Sn, Al bimetallic auxiliary agent, low Sn/Pt ratio, formed alumina and be
The high activity of carrier, highly selective and reaction stability catalyst have apparent Social benefit and economic benefit.
In catalyst prepared by the present invention for preparing propylene by dehydrogenating propane, using formed alumina as carrier, with the IVth race
Metal element, group III element metal are bimetallic auxiliary agent, using platinum family element metal as dehydrogenation active component.
Provided by the present invention for the preparation method of the catalyst of preparing propylene by dehydrogenating propane, process are as follows:
(1) alumina support is put into containing auxiliary agent group III element metal salt and the IVth race's element gold using co-impregnation
In the solution for belonging to salt, 2-12h is impregnated.Catalyst carrier is obtained after 60-150 DEG C of dry 2-12h, 400-700 DEG C of roasting 10-15h.
(2) vacuum impregnation technology is used, the active component of supported catalyst in the catalyst carrier obtained in step (1).
By 60-150 DEG C of sample dry 2-12h, 400-700 DEG C of roasting 2-6h.
(3) then the product of above-mentioned steps (2) impregnates nitrate at 400-700 DEG C of progress steam treatment dechlorination 2-6h
Solution introduces alkali metal promoter, by 60-150 DEG C of sample dry 2-12h, 400-700 DEG C of roasting 3-6h.
(4) product of above-mentioned steps (3) impregnates hydrochloric acid, 60-150 DEG C of dry 2-12h, 400-700 DEG C of roasting 2-6h.Then
Vulcanized with ammonium sulfide, 60-150 DEG C of dry 2-12h.
IVth race's metal element salt described in step (1) is one of nitrate or chloride of germanium or tin or several
Kind, the group III element metal salt is one of nitrate or chloride of aluminium or several.
The active component of catalyst described in step (2) is one of platinum family element metal platinum, palladium, iridium, lawrencium or osmium
Or several combination；When above-mentioned active component is platinum, platinum source used is one in chloroplatinic acid, platinum ammonia or acetylacetone,2,4-pentanedione oxygen platinum
Kind or two kinds or more, when active component is palladium, iridium, lawrencium or osmium, source metal uses corresponding metal chloride or organic complex
Object.
Mass Calculation based on alumina support, in auxiliary agent the mass percentage of the IVth race's metal element be 0.001~
2.5wt.%, the mass percentage of group III element metal are 0.001~5wt.%, and the active component of catalyst is Pt metal
Mass percentage is 0.1~0.8wt.%.
The mass ratio of auxiliary agent group III element metal described in step (1) and the IVth race's metal element is 0.0~10.0.
Alumina support described in step (1) is alumina globule, the aluminium oxide of bar shaped or graininess SB powder.
The mass ratio of IVth race's metal element auxiliary agent and active component platinum family element metal is 0~1.5.
Sn and Al are introduced into alumina support in a manner of co-impregnation, and dehydrogenation active component Pt race metallic element passes through vacuum
Infusion process introduces carrier.
Auxiliary agent described in step 1 is that the IVth race's metal element is selected from one of germanium, tin or several combinations and the
III race's metal element is selected from the metallic combination of one or more of silicon source.Salting liquid used can be nitrate and chlorination
Object, such as SnCl4、SnCl2、Al(NO3)3、AlCl3Deng.
Alumina support described in step 1 includes several alumina globules, the domestic several oxygen that offshore company provides
Change aluminium bead, self-control bar shaped aluminium oxide and self-control graininess SB powder.
In above-mentioned technical proposal, preferred 110-130 DEG C of drying temperature, drying time preferred 5-7h of step (1), maturing temperature
It is preferred that 500-600 DEG C, the preferred 11-13h of calcining time；Step (2), (3), preferred 110-130 DEG C of drying temperature of (4), it is dry
Time preferred 5-7h, preferred 500-600 DEG C of maturing temperature, the preferred 3-5h of calcining time；The dechlorination treatment temperature of step (3) is preferred
500-600 DEG C, dechlorination time preferred 4-5h.
Catalyst for preparing propylene with propane dehydrogenation of the present invention uses fluidized bed, moving bed or fixed bed reactors,
It is preferred that fixed bed reactors.Reaction condition: normal pressure；Reaction temperature is 620 DEG C；The mass space velocity of propane is 6.0h-1；Hydrogen-hydrocarbon ratio is
1.0；Product analysis using the propane-propylene content in gas-chromatography on-line analysis dehydrogenation product, and calculate reaction conversion ratio,
The selectivity and yield of propylene.
The invention has the characteristics that
(1) Sn can be made in carrier by the introducing of co-impregnation method in the form of double auxiliary agents Al and Sn on the alumina support
In spreaded more evenly across with atomic level, be conducive to its abundant effect with carrier.Al the and Sn auxiliary agent roasting that co-impregnation introduces
Forming fresh aluminium oxide island later can be used as bridge, greatly increase the active force between auxiliary agent Sn atom and alumina support,
Be conducive to inhibit Sn4+It is reduced into zeroth order Sn0, to improve the selectivity of the dehydrogenation activity of catalyst, stability and propylene.
It can be found that being carrier, co-impregnation Sn-Al using the alumina globule that different company provides as shown in attached drawing 1,2
Auxiliary agent is made, conversion ratio, selectivity and the stability that supporting Pt does the propane dehydrogenation catalyst of the active component preparation of catalyst are equal
It significantly improves.
(2) using the aluminium oxide that Sn, Al are bimetallic auxiliary agent as carrier, infusion process load platinum family metal element, the IIIth race and
The catalyst of preparing propylene by dehydrogenating propane is made in IVth race's element.Al, Sn bimetallic auxiliary agent island in the catalyst of this method preparation
Be conducive to improve platinum family element active component and carrier active force and its carrier surface dispersion degree and stability, thus
Prevent the reunion of dehydrogenation activity metal during the reaction.The Al auxiliary agent impregnated after on alumina support can form fresh oxidation
Aluminium island improves metal-auxiliary agent-carrier and directly interacts, to improve the selectivity of the dehydrogenation activity of catalyst, alkene
With the stability of catalyst.
(3) the superpower interaction of Sn/Pt ratio and the two ultralow in the present invention effectively reduces in reaction process
Sn4+It is reduced into metal Sn, to be conducive to the raising of catalyst activity, stability and selectivity.
(4) carrier of catalyst selects molding alumina globule, the alumina globule have big aperture, specific surface and
High thermal stability, and eliminate carrier forming process.Auxiliary agent, which introduces, in carrier uses known infusion process, operation letter
It is single.
Detailed description of the invention
The conversion of propane of Fig. 1 Pt-Sn-Al/ alumina globule A catalyst dehydrogenating propane reaction, Propylene Selectivity and third
Alkene yield.Evaluation condition: catalyst quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane body
Product is than being 1:1.
The conversion of propane of Fig. 2 Pt-Sn-Al/ alumina globule B catalyst dehydrogenating propane reaction, Propylene Selectivity and third
Alkene yield.Evaluation condition: catalyst quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane body
Product is than being 1:1.
Specific embodiment
Embodiment 1
Infusion process prepares Sn-Al/Al2O3Carrier.Take 2ml Al (NO3)3(0.05gAl/ml) solution and 2.44ml
(0.025gSn/ml)SnCl4Dilute hydrochloric acid solution be put into 200ml beaker, be added 20ml deionized water, be uniformly mixed.It weighs
Aluminium oxide A bead 10g is added in above-mentioned solution, places absorption 4h.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 12h are obtained
To the catalyst carrier of double auxiliary agents.
It takes the above-mentioned carrier of 10g to be put into 250ml bottle,suction, vacuumizes 0.5h.The chlorine platinum of 1.35ml (0.037gPt/ml) is added
10% dilute hydrochloric acid of acid solution and 2.4ml.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.
Then by the catalyst of preparation in 550 DEG C of progress steam treatment 4h；Then 5.6ml KNO is impregnated3(0.025gK/
Ml) solution introduces alkali metal promoter, by 120 DEG C of sample dry 4h, 550 DEG C of roasting 4h；Impregnate dilute salt of 1.2ml HCl (10%)
Acid, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Then 1.0ml (NH is used4)2S (2%) ammonium sulfide is vulcanized, and 120 DEG C sufficiently dry
It is spare after 4h.
Evaluation condition: catalyst reacts preceding hydrogen in dehydrogenating propane, and 480 DEG C of reductase 12 h are reacted for dehydrogenating propane.It urges
Agent quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane volume ratio is 1:1.
Reaction result is as follows: after reaction 10h, the alumina globule of Al-Sn bimetallic auxiliary agent is the dehydrogenating propane system of carrier
The conversion of propane of propylene catalyst is 38.4%, Propylene Selectivity 92.9%, and productivity of propylene is 35.7% (table 1).
Embodiment 2
Infusion process prepares Sn-Al/Al2O3Carrier.Take 4.5ml Al (NO3)3(0.05gAl/ml) solution and 2.44ml
(0.025gSn/ml)SnCl4Dilute hydrochloric acid solution be put into 200ml beaker, be added 20ml deionized water, be uniformly mixed.It weighs
Aluminium oxide A bead 10g is added in above-mentioned solution, places absorption 4h.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 12h are obtained
To the catalyst carrier of double auxiliary agents.
It takes the above-mentioned carrier of 10g to be put into 250ml bottle,suction, vacuumizes 0.5h.The chlorine platinum of 1.35ml (0.037gPt/ml) is added
10% dilute hydrochloric acid of acid solution and 2.4ml.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.
Then by the catalyst of preparation in 550 DEG C of progress steam treatment 4h；Then 5.6ml KNO is impregnated3(0.025gK/
Ml) solution introduces alkali metal promoter, by 120 DEG C of sample dry 4h, 550 DEG C of roasting 4h；Impregnate dilute salt of 1.2ml HCl (10%)
Acid, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Then 1.0ml (NH is used4)2S (2%) ammonium sulfide is vulcanized, and 120 DEG C sufficiently dry
It is spare after 2h.
Evaluation condition: catalyst reacts preceding hydrogen in dehydrogenating propane, and 480 DEG C of reductase 12 h are reacted for dehydrogenating propane.It urges
Agent quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane volume ratio is 1:1.
Reaction result is as follows: after reaction 10h, the alumina globule of Al-Sn bimetallic auxiliary agent is the dehydrogenating propane system of carrier
The conversion of propane of propylene catalyst is 39.2%, Propylene Selectivity 92.6%, and productivity of propylene is 36.3% (table 1).
Embodiment 3
Infusion process prepares Sn-Al/Al2O3Carrier.Take 9ml Al (NO3)3(0.05gAl/ml) solution and 2.44ml
(0.025gSn/ml)SnCl4Dilute hydrochloric acid solution be put into 200ml beaker, be added 20ml deionized water, be uniformly mixed.It weighs
Aluminium oxide A bead 10g is added in above-mentioned solution, places absorption 4h.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 12h are obtained
To the catalyst carrier of double auxiliary agents.
It takes the above-mentioned carrier of 10g to be put into 250ml bottle,suction, vacuumizes 0.5h.The chlorine platinum of 1.35ml (0.037gPt/ml) is added
10% dilute hydrochloric acid of acid solution and 2.4ml.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.
Then by the catalyst of preparation in 550 DEG C of progress steam treatment 4h；Then 5.6ml KNO is impregnated3(0.025gK/
Ml) solution introduces alkali metal promoter, by 120 DEG C of sample dry 4h, 550 DEG C of roasting 4h；Impregnate dilute salt of 1.2ml HCl (10%)
Acid, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Then 1.0ml (NH is used4)2S (2%) ammonium sulfide is vulcanized, and 120 DEG C sufficiently dry
It is spare after 4h.
Evaluation condition: catalyst reacts preceding hydrogen in dehydrogenating propane, and 480 DEG C of reductase 12 h are reacted for dehydrogenating propane.It urges
Agent quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane volume ratio is 1:1.
Reaction result is as follows: after reaction 10h, the alumina globule of Al-Sn bimetallic auxiliary agent is the dehydrogenating propane system of carrier
The conversion of propane of propylene catalyst is 37.6%, Propylene Selectivity 93.9%, and productivity of propylene is 35.3% (table 1).
Comparative example 1
In order to be carried out with the alumina globule of Al-Sn bimetallic auxiliary agent for the catalyst for preparing propylene with propane dehydrogenation performance of carrier
Compare, infusion process prepares Pt-Sn/Al2O3Carrier.Take 2.44ml (0.025gSn/ml) SnCl4Dilute hydrochloric acid solution be put into 200ml
In beaker, 20ml deionized water is added, is uniformly mixed.It weighs aluminium oxide A bead 10g to be added in above-mentioned solution, places absorption 4h.
60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 12h obtain the catalyst carrier of monometallic auxiliary agent.
It takes the above-mentioned carrier of 10g to be put into 250ml bottle,suction, vacuumizes 0.5h.The chlorine platinum of 1.35ml (0.037gPt/ml) is added
10% dilute hydrochloric acid of acid solution and 2.4ml.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.
Then by the catalyst of preparation in 550 DEG C of progress steam treatment 4h；Then 5.6ml KNO is impregnated3(0.025gK/
Ml) solution introduces alkali metal promoter, by 120 DEG C of sample dry 4h, 550 DEG C of roasting 4h；Impregnate dilute salt of 1.2ml HCl (10%)
Acid, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Then 1.0ml (NH is used4)2S (2%) ammonium sulfide is vulcanized, and 120 DEG C sufficiently dry
It is spare after 2h.
Evaluation condition: catalyst reacts preceding hydrogen in dehydrogenating propane, and 480 DEG C of reductase 12 h are reacted for dehydrogenating propane.It urges
Agent quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane volume ratio is 1:1.
Reaction result is as follows: after reaction 10h, the alumina globule of Al-Sn bimetallic auxiliary agent is the dehydrogenating propane system of carrier
The conversion of propane of propylene catalyst is 36.2%, Propylene Selectivity 88.8%, and productivity of propylene is 32.2% (table 1).
Table 1Pt-Sn-Al/ alumina globule A catalyst dehydrogenating propane react the conversion of propane of 10h, Propylene Selectivity and
Productivity of propylene.Evaluation condition: catalyst quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane
Volume ratio is 1:1.
Embodiment 4
Infusion process prepares Sn-Al/Al2O3Carrier.Take 2ml Al (NO3)3(0.05gAl/ml) solution and 2.44ml
(0.025gSn/ml)SnCl4Dilute hydrochloric acid solution be put into 200ml beaker, be added 20ml deionized water, be uniformly mixed.It weighs
Aluminium oxide B bead 10g is added in above-mentioned solution, places absorption 4h.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 12h are obtained
To the catalyst carrier of double auxiliary agents.
It takes the above-mentioned carrier of 10g to be put into 250ml bottle,suction, vacuumizes 0.5h.The chlorine platinum of 1.35ml (0.037gPt/ml) is added
10% dilute hydrochloric acid of acid solution and 2.4ml.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.
Then by the catalyst of preparation in 550 DEG C of progress steam treatment 4h；Then 5.6ml KNO is impregnated3(0.025gK/
Ml) solution introduces alkali metal promoter, by 120 DEG C of sample dry 4h, 550 DEG C of roasting 4h；Impregnate dilute salt of 1.2ml HCl (10%)
Acid, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Then 1.0ml (NH is used4)2S (2%) ammonium sulfide is vulcanized, and 120 DEG C sufficiently dry
It is spare after 4h.
Evaluation condition: catalyst reacts preceding hydrogen in dehydrogenating propane, and 480 DEG C of reductase 12 h are reacted for dehydrogenating propane.It urges
Agent quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane volume ratio is 1:1.
Reaction result is as follows: after reaction 10h, the alumina globule of Al-Sn bimetallic auxiliary agent is the dehydrogenating propane system of carrier
The conversion of propane of propylene catalyst is 37.8%, Propylene Selectivity 91.4%, and productivity of propylene is 34.5% (table 2).
Embodiment 5
Infusion process prepares Sn-Al/Al2O3Carrier.Take 4.5ml Al (NO3)3(0.05gAl/ml) solution and 2.44ml
(0.025gSn/ml)SnCl4Dilute hydrochloric acid solution be put into 200ml beaker, be added 20ml deionized water, be uniformly mixed.It weighs
Aluminium oxide B bead 10g is added in above-mentioned solution, places absorption 4h.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 12h are obtained
To the catalyst carrier of double auxiliary agents.
It takes the above-mentioned carrier of 10g to be put into 250ml bottle,suction, vacuumizes 0.5h.The chlorine platinum of 1.35ml (0.037gPt/ml) is added
10% dilute hydrochloric acid of acid solution and 2.4ml.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.
Then by the catalyst of preparation in 550 DEG C of progress steam treatment 4h；Then 5.6ml KNO is impregnated3(0.025gK/
Ml) solution introduces alkali metal promoter, by 120 DEG C of sample dry 4h, 550 DEG C of roasting 4h；Impregnate dilute salt of 1.2ml HCl (10%)
Acid, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Then 1.0ml (NH is used4)2S (2%) ammonium sulfide is vulcanized, and 120 DEG C sufficiently dry
It is spare after 4h.
Evaluation condition: catalyst reacts preceding hydrogen in dehydrogenating propane, and 480 DEG C of reductase 12 h are reacted for dehydrogenating propane.It urges
Agent quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane volume ratio is 1:1.
Reaction result is as follows: after reaction 10h, the alumina globule of Al-Sn bimetallic auxiliary agent is the dehydrogenating propane system of carrier
The conversion of propane of propylene catalyst is 36.7%, Propylene Selectivity 93.6%, and productivity of propylene is 34.3% (table 2).
Embodiment 6
Infusion process prepares Sn-Al/Al2O3Carrier.Take 9ml Al (NO3)3(0.05gAl/ml) solution and 2.44ml
(0.025gSn/ml)SnCl4Dilute hydrochloric acid solution be put into 200ml beaker, be added 20ml deionized water, be uniformly mixed.It weighs
Aluminium oxide B bead 10g is added in above-mentioned solution, places absorption 4h.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 12h are obtained
To the catalyst carrier of double auxiliary agents.
It takes the above-mentioned carrier of 10g to be put into 250ml bottle,suction, vacuumizes 0.5h.The chlorine platinum of 1.35ml (0.037gPt/ml) is added
10% dilute hydrochloric acid of acid solution and 2.4ml.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.
Then by the catalyst of preparation in 550 DEG C of progress steam treatment 4h；Then 5.6ml KNO is impregnated3(0.025gK/
Ml) solution introduces alkali metal promoter, by 120 DEG C of sample dry 4h, 550 DEG C of roasting 4h；Impregnate dilute salt of 1.2ml HCl (10%)
Acid, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Then 1.0ml (NH is used4)2S (2%) ammonium sulfide is vulcanized, and 120 DEG C sufficiently dry
It is spare after 2h.
Evaluation condition: catalyst reacts preceding hydrogen in dehydrogenating propane, and 480 DEG C of reductase 12 h are reacted for dehydrogenating propane.It urges
Agent quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane volume ratio is 1:1.
Reaction result is as follows: after reaction 10h, the alumina globule of Al-Sn bimetallic auxiliary agent is the dehydrogenating propane system of carrier
The conversion of propane of propylene catalyst is 36.5%, Propylene Selectivity 94.2%, and productivity of propylene is 34.4% (table 2).
Table 2Pt-Sn-Al/ alumina globule B catalyst dehydrogenating propane react the conversion of propane of 10h, Propylene Selectivity and
Productivity of propylene.Evaluation condition: catalyst quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane
Volume ratio is 1:1.
Comparative example 2
In order to be carried out with the alumina globule of Al-Sn bimetallic auxiliary agent for the catalyst for preparing propylene with propane dehydrogenation performance of carrier
Compare, infusion process prepares Pt-Sn/Al2O3Carrier.Take 2.44ml (0.025gSn/ml) SnCl4Dilute hydrochloric acid solution be put into 200ml
In beaker, 20ml deionized water is added, is uniformly mixed.It weighs aluminium oxide B bead 10g to be added in above-mentioned solution, places absorption 4h.
60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 12h obtain the catalyst carrier of monometallic auxiliary agent.
It takes the above-mentioned carrier of 10g to be put into 250ml bottle,suction, vacuumizes 0.5h.The chlorine platinum of 1.35ml (0.037gPt/ml) is added
10% dilute hydrochloric acid of acid solution and 2.4ml.60 DEG C of dry 4h, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.
Then by the catalyst of preparation in 550 DEG C of progress steam treatment 4h；Then 5.6ml KNO is impregnated3(0.025gK/
Ml) solution introduces alkali metal promoter, by 120 DEG C of sample dry 4h, 550 DEG C of roasting 4h；Impregnate dilute salt of 1.2ml HCl (10%)
Acid, 120 DEG C of dry 4h, 550 DEG C of roasting 4h.Then 1.0ml (NH is used4)2S (2%) ammonium sulfide is vulcanized, and 120 DEG C sufficiently dry
It is spare after 3h.
Evaluation condition: catalyst reacts preceding hydrogen in dehydrogenating propane, and 480 DEG C of reductase 12 h are reacted for dehydrogenating propane.It urges
Agent quality 1.9g, propane mass space velocity 6h-1, normal pressure, 620 DEG C of reaction temperature, hydrogen/propane volume ratio is 1:1.
Reaction result is as follows: after reaction 10h, the alumina globule of Al-Sn bimetallic auxiliary agent is the dehydrogenating propane system of carrier
The conversion of propane of propylene catalyst is 35.6%, Propylene Selectivity 91.6%, and productivity of propylene is 32.6% (table 2).
Claims (9)
1. a kind of preparation method of the catalyst for preparing propylene by dehydrogenating propane, it is characterised in that: preparation process are as follows:
(1) alumina support is put into the solution of the metal salt of the metal salt containing auxiliary agent aluminium and germanium or tin using co-impregnation
In, 2-12h is impregnated, obtains catalyst carrier after 60-150 DEG C of dry 2-12h, 400-700 DEG C of roasting 10-15h；
(2) vacuum impregnation technology is used, the activity component metal of supported catalyst in the catalyst carrier obtained in step (1)
Pt, by 60-150 DEG C of sample dry 2-12h, 400-700 DEG C of roasting 2-6h；
(3) then the product of above-mentioned steps (2) impregnates nitrate solution at 400-700 DEG C of progress steam treatment dechlorination 2-6h
Alkali metal promoter is introduced, by 60-150 DEG C of sample dry 2-12h, 400-700 DEG C of roasting 3-6h；
(4) product of above-mentioned steps (3) impregnates hydrochloric acid, then 60-150 DEG C of dry 2-12h, 400-700 DEG C of roasting 2-6h use sulphur
Change ammonium to be vulcanized, 60-150 DEG C of dry 2-12h.
2. preparation method according to claim 1, it is characterised in that: the metal salt of germanium described in step (1) or tin is
One of nitrate or chloride of germanium or tin are several, and the metal salt of the aluminium is in the nitrate or chloride of aluminium
It is one or several kinds of.
3. preparation method according to claim 1, it is characterised in that: the active component of catalyst described in step (2)
For metal platinum, platinum source used is one of chloroplatinic acid, platinum ammonia or acetylacetone,2,4-pentanedione oxygen platinum or two kinds or more.
4. preparation method according to claim 1,2 or 3, it is characterised in that: the Mass Calculation based on alumina support helps
Germanium or the mass percentage of tin metal are 0.001~2.5wt.% in agent, the mass percentage of aluminum metal is 0.001~
5wt.%, the active component of catalyst are that Pt metal mass percentage is 0.1~0.8wt.%.
5. preparation method according to claim 1, it is characterised in that: auxiliary agent A l metal and germanium described in step (1) or
The mass ratio of tin metal is 0.0~10.0.
6. preparation method according to claim 1, it is characterised in that: alumina support described in step (1) is oxidation
Aluminium bead, the aluminium oxide of bar shaped or graininess SB powder.
7. preparation method according to claim 1, it is characterised in that: the tin or germanium metal promoter and active component platinum
The mass ratio of metal is 0~1.5.
8. preparation method according to claim 1, it is characterised in that: step (1) drying temperature is 110-130 DEG C,
Drying time is 5-7h, and maturing temperature is 500-600 DEG C, calcining time 11-13h；Step (2), (3), the dry temperature in (4)
Degree is 110-130 DEG C, drying time 5-7h, and maturing temperature is 500-600 DEG C, calcining time 3-5h；The dechlorination of step (3)
Treatment temperature is 500-600 DEG C, and the dechlorination time is 4-5h.
9. a kind of catalyst for preparing propylene by dehydrogenating propane of any the method preparation of claim 1-8.
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| CN108295847B (en) * | 2018-02-11 | 2020-09-08 | 四川润和催化新材料股份有限公司 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| KR20200004501A (en) * | 2018-07-04 | 2020-01-14 | 한국화학연구원 | Catalyst having enhanced conversion ratio and selectivity for manufacturing olefin, and a manufacturing method thereof |
| CN112619690A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Supported catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
| CN113893851B (en) * | 2020-07-06 | 2024-02-02 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for preparing olefin by alkane dehydrogenation |
| CN111925271B (en) * | 2020-08-17 | 2023-01-10 | 湘潭大学 | Catalytic decomposition method for preparing propylene by direct dehydrogenation of propane |
| CN114588898A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院大连化学物理研究所 | Catalyst for preparing olefin by low-carbon alkane dehydrogenation and preparation and application thereof |
| CN114621047A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Dehydrogenation method of low-carbon alkane |
| CN115703065A (en) * | 2021-08-17 | 2023-02-17 | 中国石油天然气股份有限公司 | Low temperature dehydrogenation process for hydrogenating aromatic compound |
| CN114349797B (en) * | 2021-12-21 | 2023-04-14 | 大连理工大学 | Metal cluster single crystal, synthesis method and application of low-carbon alkane in catalytic dehydrogenation |
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