CN104107718B - Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof - Google Patents
Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof, mainly solve that existing catalyst olefine selective under the high temperature conditions is low, carbon deposit serious, the problem of one way poor stability.The present invention is by a kind of loaded catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof, this catalyst is with silica-base material as carrier, with vanadium or its oxide as active component, with iron series element and IIIA race element as auxiliary agent, the method using dipping is prepared, at low O2In the way of oxidative dehydrogenation and direct dehydrogenation combine, the reaction of manufacturing olefin by low-carbon alkane dehydrogenation it is catalyzed under concentration conditions, finally carry out the technical scheme of Burning Coke on Catalyst regeneration, preferably solve this problem, can be used in the commercial production of dehydrogenating low-carbon alkane producing light olefins.
Description
Technical field
The present invention relates to a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof.
Background technology
Low-carbon alkene is widely used in plastics, synthetic rubber, medicine, gasoline additive, ion exchange resin, detergent, spice and the production of various chemical intermediate, is important Organic Chemicals.Along with the development of chemical industry, to the demand growth of low-carbon alkene quickly, develop by the low carbon alkane preparing low-carbon olefins process of added value for making full use of low-carbon alkanes resource, to open up new alkene source significant.Propylene/isobutene., essentially from Petroleum and the steam cracking of liquefied petroleum gas and the coproduction of refinery factory fluid catalytic cracking process or by-product, the most only is difficult to meet the demand that China's chemical industry is fast-developing by said method.Propane/dehydrogenation of isobutane technology has become as propylene/isobutene. source important after steam cracking and the coproduction of fluid catalytic cracking process or by-product.Present the most industrialized propane/dehydrogenation of isobutane technique includes the techniques such as the Linde of FDB-4 and the Linde company of the Oleflex technique of Uop Inc., the Star technique of Phillips company, the Catofin technique of AirProduct&Chemical company, SnamprogettiSPA company.The domestic process units still not having dehydrogenating low-carbon alkane producing light olefins.
Dehydrogenating low-carbon alkane catalytic reaction is carried out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, and the catalyst of exploitation high activity, high selectivity and high stability becomes the key of this technology.Catalyst for dehydrogenation of low-carbon paraffin can be divided into oxidative dehydrogenation and Non-oxidative dehydrogenation i.e. direct dehydrogenation two types.What what Chinese patent (CN96117222.3) and United States Patent (USP) (US4438288) were reported disclosed with catalyst that platinum element is main active component and Chinese patent (CN200910012450.1, CN200610126812.6) is two class important catalyst of low-carbon alkanes direct dehydrogenation catalytic reaction with the catalyst that chromium element is main active component.Low-carbon alkanes direct dehydrogenation process has been realized in industrial applications, but this process is limited by thermodynamical equilibrium, has that reaction temperature is high, energy consumption is big, a catalyst easily quick shortcoming such as coking deactivation, less stable.In recent years, the research of propane/isobutene for oxo-dehydrogenation is paid close attention to, process is not limited by thermodynamical equilibrium, but there is also that catalyst activity is low, target alkene selectivity is poor, deep oxidation reaction is serious, by-product is more and products distribution is difficult to the shortcomings such as control.
In recent years, catalytic component based on vanadium has obtained studying widely as the dehydrogenation of propane/iso-butane, the most existing oxidative dehydrogenation, also has Non-oxidative dehydrogenation, but dehydrogenation is the most undesirable and rapid catalyst deactivation.O.Ovsitser (O. Ao Fuxisite) etc. are at " ChemicalCommunications " (chemical communication) 2010, " the Selectiveandstableiso-buteneproductionoverhighlydisperse dVO delivered on 46,4974 4976xspeciesonSiO2Supportsviacombiningoxidativeandnon-oxidativeiso-butaned ehydrogenation " (polymolecularity VOx/SiO2The isobutene for oxo-dehydrogenation of catalyst and Non-oxidative dehydrogenation) article reports the dehydrogenation of isobutane that combines with Non-oxidative dehydrogenation of oxidative dehydrogenation of barium oxide catalysis and reacts, but the shortcoming of the method is that olefine selective is the highest under high conversion, less stable.The study find that with barium oxide for catalyst activity component, be supported on mesoporous silicon carrier with the composite assistant that iron series element and Group IIIA element are composition, the beneficially performance of catalyst electronic effect, thus improve catalyst choice and one way stability.On the other hand, at low O2Under the aerobic conditions of content, in the way of oxidative dehydrogenation and non-oxide direct dehydrogenation combine, it is catalyzed the reaction of low-carbon alkanes alkene, contributes to reducing the generation of carbon deposit, make catalyst have more preferable activity, selectivity and life-span, reduce catalytic dehydrogenation processes cost.
Summary of the invention
The technical problem to be solved is that existing catalyst olefine selective under the high temperature conditions is low, carbon deposit serious, the problem of one way poor stability, a kind of new catalyst for dehydrogenating low-carbon alkane producing light olefins is provided, this method for preparing catalyst is easy, units activity component effective rate of utilization is high, have when using under the high temperature conditions, the advantage that catalyst olefine selective is high, coking deactivation speed is slow, catalyst stability is high.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterised in that: comprise following components by weight percentage:
A) with silica-base material as carrier, carrier is the 80～98.5% of catalyst weight；
B) with the oxide of V as active component, described active component is the 1～10% of catalyst weight;
C) with the oxide of iron series element and Group IIIA element as auxiliary agent, the oxide of described iron series element is the 0.1～10% of catalyst weight, oxide is catalyst weight the 0.1～1.0% of described Group IIIA element.
In technique scheme, the preferred version of silicon substrate carrier is the one in SBA-15, MCM-41, MCM-48 or amorphous silica, for the 80～98.5% of catalyst weight；Barium oxide is catalyst activity component, and for the 1～10% of catalyst weight, preferably scope is 3～8%；At least one in Fe, Co and Ni of iron series element auxiliary agent, it is 0.5～5% that the oxide of iron series element accounts for the preferred scope of catalyst weight；At least one in Ga, In and Tl of Group IIIA element auxiliary agent, it is 0.1～0.6% that the oxide of Group IIIA element accounts for the preferred scope of catalyst weight.
A kind of method for preparing catalyst for manufacturing olefin by low-carbon alkane dehydrogenation involved in the present invention, can use following steps:
1) being firstly added in the soluble salt solutions of auxiliary agent by silicon substrate carrier, assistant concentration is 0.05～5mol/L, and dipping temperature is 10oC～80oC, dip time is 1～24 hour；
2) silicon substrate carrier after step 1) being impregnated is dried, roasting, and baking temperature is 90oC～150oC, drying time is 1～24 hour, and sintering temperature is 400oC～650oC, roasting time is 1～24 hour；
3) by step 2) dipping after silicon substrate carrier be then added in the soluble salt solutions of active component, the concentration of active component is 0.05～5mol/L, and dipping temperature is 10oC～80oC, dip time is 1～24 hour；
4) silicon substrate carrier after step 3) being impregnated is dried, roasting, obtains corresponding loaded catalyst, and wherein baking temperature is 90oC～150oC, drying time is 1～24 hour, and sintering temperature is 400oC～650oC, roasting time is 1～24 hour.
In technique scheme, immersion solvent uses water or benzene, toluene, methanol, acetone, at least one in acetonitrile.The soluble-salt of iron series element and Group IIIA element auxiliary agent is selected from least one in chloride, nitrate or acetate.
The another kind of method for preparing catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, can use following steps:
1) being added by silicon substrate carrier in the mixed solution of soluble-salt of active component and auxiliary agent, active component concentration 0.05～5mol/L, assistant concentration is 0.05～5mol/L, and dipping temperature is 10oC～80oC, dip time is 1～24 hour；
2) silicon substrate carrier after step 1) being impregnated is dried, roasting, obtains corresponding loaded catalyst, and wherein baking temperature is 90oC～150oC, drying time is 1～24 hour, and sintering temperature is 400oC～650oC, roasting time is 1～24 hour.
In technique scheme, immersion solvent uses water or benzene, toluene, methanol, acetone, at least one in acetonitrile.The soluble-salt of iron series element and Group IIIA element auxiliary agent is selected from least one in chloride, nitrate or acetate.
Catalyst involved in the present invention application in manufacturing olefin by low-carbon alkane dehydrogenation, can use and comprise following processing step:
1) catalyst pretreatment: by catalyst in atmosphere 400oC～600oC processes 0.5～10 hour；
2) catalytic dehydrogenation: with low-carbon alkanes and O2For raw material, low-carbon alkanes and O2Volume ratio is 20:1～8:1, carries out catalytic oxidative dehydrogenation and catalytic dehydrogenating reaction in the reactor, and reaction temperature is 400oC～600oC, reaction pressure is 0.08MPa～0.12MPa, and alkane mass space velocity is 3.0～8.0h-1, reactor is to include the one in fixed bed, fluid bed or moving bed；
3) catalyst regeneration: reacted decaying catalyst carries out coke-burning regeneration, can use in-situ regeneration or ex-situ regeneration, and regeneration temperature is 400oC～650oC, the recovery time is 1～10 hour, and regeneration atmosphere includes at least one in oxygen, air, carbon dioxide or steam.
In technique scheme, the carrier gas of low-carbon alkanes or regeneration atmosphere is selected from N2Or at least one in Ne.Dehydrogenating propane reaction temperature is 400oC～580oC；Dehydrogenation of isobutane reaction temperature is 450oC～600oC, preferred reaction temperature is 520oC～550oC。
Compared with prior art, the present invention has significant advantage and salience effect, and silica-base material is relatively strong to the absorbability of active component presoma, has high-specific surface area and moderate surface acidity；With barium oxide for catalyst activity component, it is to avoid the use of noble metal；The composite assistant being composition with iron series element and Group IIIA element, the beneficially performance of catalyst electronic effect, the activity of catalyst can be played good facilitation, thus improve catalyst choice and one way stability.On the other hand, at low O2Under the aerobic conditions of content, in the way of oxidative dehydrogenation and non-oxide direct dehydrogenation combine, it is catalyzed the reaction of low-carbon alkanes alkene, contributes to reducing the generation of carbon deposit, make catalyst have more preferable activity, selectivity and life-span, reduce catalytic dehydrogenation processes cost.
Dehydrogenating low-carbon alkane reaction is carried out on the flowing miniature catalyst reaction device of quartz tube reactor continuously.Carrier gas is He；Product analysis uses HP-5890 gas chromatograph (HP-AL/S capillary column, 50m × 0.53mm × 15 μm；Fid detector) alkane in on-line analysis dehydrogenation product, olefin(e) centent calculate the conversion ratio of reaction, selectivity and yield.The catalyst prepared of method using the present invention to provide reacts for dehydrogenating low-carbon alkane, and propane/iso-butane conversion ratio reaches 40%/50%, olefine selective is higher than 90%；Through 10 coke-burning regenerations, iso-butane conversion ratio is maintained at 45%, olefine selective be higher than 90%, catalyst performance stabilised, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
First 100gMCM-41 is joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of Thallous nitrate. 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Co oxide is the 2.5% of catalyst weight, and the load capacity of Tl oxide is the 0.2% of catalyst weight.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst A.Catalyst composition is listed in table 3, and test result is listed in table 4.
[embodiment 2]
First the mixed solution of ammonium metavanadate, cobalt nitrate and Thallous nitrate. is prepared.Then 100gSi-MCM-41 is joined above-mentioned solution in 80oC impregnates 2 hours, and making the content of barium oxide in catalyst is the 5% of catalyst weight, and the load capacity of cobalt is calculated as the 2.5% of catalyst weight with cobalt oxide, and the load capacity of thallium is calculated as the 0.2% of catalyst weight with oxide, then by the sample after dipping in an oven 120oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst B.
[embodiment 3]
First 100gMCM-41 is joined in the aqueous solution of cobalt nitrate 0.05mol/L in 10oC impregnates 24 hours, in 10 in the aqueous solution of Thallous nitrate. 0.05mol/LoC impregnates 24 hours, and in catalyst, the load capacity of Co is calculated as the 0.1% of catalyst weight with oxide, and the load capacity of Tl is calculated as the 0.1% of catalyst weight with oxide.Then by the sample in an oven 90 after dippingoC is dried 24 hours.Dried sample again in Muffle furnace in 400oRoasting 24 hours under C.Next by the sample after roasting 0.05mol/L ammonium metavanadate 10oC aqueous solution impregnates 24 hours, makes V oxide content is catalyst weight 1% in catalyst, then by the sample after dipping in an oven 90oC is dried 24 hours, dried sample again in Muffle furnace in 400oRoasting 24 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 400oProcess 10 hours under C, obtain catalyst C.
[embodiment 4]
First 100gMCM-41 is joined in the aqueous solution of cobalt nitrate 5mol/L in 80oC impregnates 1 hour, in 80 in the aqueous solution of Thallous nitrate. 0.5mol/LoC impregnates 1 hour, and in catalyst, the load capacity of Co is calculated as the 10% of catalyst weight with oxide, and the load capacity of Tl is calculated as the 1.0% of catalyst weight with oxide.Then by the sample in an oven 150 after dippingoC is dried 1 hour.Dried sample again in Muffle furnace in 650oRoasting 1 hour under C.Next by the sample after roasting 0.5mol/L ammonium metavanadate 80oC aqueous solution impregnates 1 hour, makes V oxide content is catalyst weight 10% in catalyst, then by the sample after dipping in an oven 150oC is dried 1 hour, dried sample again in Muffle furnace in 650oRoasting 2 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 600oProcess 0.5 hour under C, obtain catalyst D.
[embodiment 5]
First the mixed solution of ammonium metavanadate, cobalt nitrate and Thallous nitrate. is prepared.Then 100gMCM-48 is joined above-mentioned solution in 80oC impregnates 2 hours, and making barium oxide content in catalyst is the 5% of catalyst weight, and the load capacity of cobalt is calculated as the 2.5% of catalyst weight with oxide, and the load capacity of thallium is calculated as the 0.2% of catalyst weight with oxide, then by the sample after dipping in an oven 120oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst E.
[embodiment 6]
First 100gSBA-15 is joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of Thallous nitrate. 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Co is calculated as the 2.5% of catalyst weight with oxide, and the load capacity of Tl is calculated as the 0.2% of catalyst weight with oxide.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst F.
[embodiment 7]
First by 100g amorphous Si2O joins in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of Thallous nitrate. 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Co is calculated as the 2.5% of catalyst weight with oxide, and the load capacity of Tl is calculated as the 0.2% of catalyst weight with oxide.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst G.
[embodiment 8]
First 100gMCM-41 is joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of indium nitrate 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Co is calculated as the 2.5% of catalyst weight with oxide, and the load capacity of In is calculated as the 0.2% of catalyst weight with oxide.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst H.
[embodiment 9]
First 100gMCM-41 is joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of Ganite (Fujisawa). 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Co is calculated as the 2.5% of catalyst weight with oxide, and the load capacity of Ga is calculated as the 0.2% of catalyst weight with oxide.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst I.
[embodiment 10]
First 100gMCM-41 is joined in the aqueous solution of nickel nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of thallium nitrate 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Ni is calculated as the 2.5% of catalyst weight with oxide, and the load capacity of Tl is calculated as the 0.2% of catalyst weight with oxide.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst J.
[embodiment 11]
First 100gMCM-41 is joined in the aqueous solution of ferric nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of indium nitrate 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Fe is calculated as the 2.5% of catalyst weight with oxide, and the load capacity of In is calculated as the 0.2% of catalyst weight with oxide.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst K.
[embodiment 12]
First 100gMCM-41 is joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of Thallous nitrate. 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Co is calculated as the 5.0% of catalyst weight with oxide, and the load capacity of Tl is calculated as the 0.6% of catalyst weight with oxide.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 8.0% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst L.
[embodiment 13]
First 100gMCM-41 is joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of Thallous nitrate. 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Co is calculated as the 0.5% of catalyst weight with oxide, and the load capacity of Tl is calculated as the 0.1% of catalyst weight with oxide.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 3.0% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst M.
[embodiment 14]
First 100g silica MCM-41 is joined containing 0.5mol/L ferric nitrate, 0.5mol/L cobalt nitrate, 0.5mol/L nickel nitrate aqueous solution in 60oC impregnates 2 hours, then in 60 in the aqueous solution containing 0.1mol/L Ganite (Fujisawa)., 0.1mol/L indium nitrate and 0.1mol/L Thallous nitrate.oC impregnates 2 hours, and in catalyst, the oxide carried amount of Fe, Co, Ni is respectively the 2.5% of catalyst weight, and the oxide carried amount of Ga, Tl, In is respectively the 0.2% of catalyst weight.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst n.
[embodiment 15]
First 100gMCM-41 is joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, in 60 in the aqueous solution of Thallous nitrate. 0.1mol/LoC impregnates 2 hours, and in catalyst, the load capacity of Co oxide is the 2.5% of catalyst weight, and the load capacity of Tl oxide is the 0.2% of catalyst weight.Then by the sample in an oven 110 after dippingoC is dried 4 hours.Dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, at the 60 of the magnesium nitrate of 0.5mol/LoImpregnating 4 hours in C aqueous solution, make V oxide content is catalyst weight 5% in catalyst, Mg oxide content is the 2% of catalyst weight, then by the sample in an oven 100 after dippingoC is dried 4 hours, dried sample again in Muffle furnace in 650oRoasting 2 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 600oProcess 1 hour under C, obtain catalyst O.
[comparative example 1]
100gMCM-41 is joined 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5.0% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst P.
[comparative example 2]
100gMCM-41 is joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60oC impregnates 2 hours, and in catalyst, the load capacity of Co is calculated as the 2.5% of catalyst weight with oxide, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Next by the sample after roasting 0.3mol/L ammonium metavanadate 60oC aqueous solution impregnates 4 hours, makes V oxide content is catalyst weight 5.0% in catalyst, then by the sample after dipping in an oven 110oC is dried 4 hours, dried sample again in Muffle furnace in 600oRoasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in atmosphere 550oProcess 2 hours under C, obtain catalyst Q.
[embodiment 16]
Catalytic reaction condition
Weigh 0.5g catalyst A and carry out dehydrogenation of isobutane evaluation.Alkane carrier gas is He, different temperature, pressure, under the conditions of carry out activity rating, test result is listed in table 1, reacts the data of 6 hours.
The dehydrogenation of isobutane catalytic condition * of table 1. catalyst A
* the reaction iso-butane conversion ratio of 6 hours and selective isobutene
[embodiment 17]
Weigh 0.5g catalyst A and carry out dehydrogenating propane evaluation.Feeding gas is propane: O2: He=20:1:79；Temperature 550oC；Normal pressure；Alkane mass space velocity is 4.6h-1Under the conditions of carry out activity rating, test result is listed in table 2.
Table 2 catalyst A is catalyzed dehydrogenating propane
| Response time (h) | Conversion of propane (%) | Propylene Selectivity (%) |
| 6 | 40.6 | 92.9 |
| 10 | 40.1 | 92.9 |
| 40 | 38.1 | 92.4 |
[embodiment 18]
Weigh 0.5g catalyst A～Q and carry out dehydrogenation of isobutane evaluation.Feeding gas is iso-butane: O2: He=20:1:79；Temperature 550oC；Normal pressure；Alkane mass space velocity is 4.6h-1Under the conditions of carry out activity rating, catalyst composition is listed in table 3, and test result is listed in table 4.
The composition of table 3 catalyst
Table 4 catalyst carries out dehydrogenation of isobutane
[comparative example 3]
Catalyst regenerating stability contrasts
Weigh 0.5g catalyst A, 0.5g catalyst P and 0.5g catalyst Q respectively and carry out dehydrogenation of isobutane evaluation.Feeding gas is iso-butane: O2: He=20:1:79；Temperature 550oC；Normal pressure；Alkane mass space velocity is 4.6h-1Under the conditions of carry out catalytic dehydrogenation, after feeding 50 hours, 560oCoke-burning regeneration 5 hours under C air atmosphere, the 6 hours performances of catalyst reaction after circular response/regeneration 10 times are listed in table 5.
Table 5 catalyst regenerating stability contrasts
Claims (10)
1. the catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterised in that: comprise following components by weight percentage:
A) with silica-base material as carrier, carrier is the 80～98.5% of catalyst weight；
B) with the oxide of V as active component, described active component is the 1～10% of catalyst weight;
C) with the oxide of iron series element and Group IIIA element as auxiliary agent, the oxide of described iron series element is the 0.1～10% of catalyst weight, oxide is catalyst weight the 0.1～1.0% of described Group IIIA element.
The most according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterised in that described low-carbon alkanes is propane or iso-butane.
The most according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterised in that described silica-base material carrier one in SBA-15, MCM-41, MCM-48 or amorphous silica.
The most according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterised in that with the oxide of V as active component, described active component is the 3～8% of catalyst weight.
The most according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterised in that at least one in Fe, Co and Ni of described iron series element auxiliary agent, the oxide of iron series element is the 0.5～5% of catalyst weight.
6. according to the catalyst being used for manufacturing olefin by low-carbon alkane dehydrogenation described in any one of Claims 1 to 5, it is characterised in that at least one in Ga, In and Tl of described Group IIIA element auxiliary agent, the oxide of Group IIIA element is the 0.1～0.6% of catalyst weight.
7. it is used for the preparation method of the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation described in claim 1, it is characterised in that preparation method comprises the steps of
1) being firstly added in the soluble salt solution of auxiliary agent by silicon substrate carrier, assistant concentration is 0.05～5mol/L, and dipping temperature is 10 DEG C～80 DEG C, and dip time is 1～24 hour；
2) silicon substrate carrier after step 1) being impregnated is dried, roasting, and baking temperature is 90 DEG C～150 DEG C, and drying time is 1～24 hour, and sintering temperature is 400 DEG C～650 DEG C, and roasting time is 1～24 hour；
3) by step 2) dipping after silicon substrate carrier be then added in the soluble salt solution of active component, the concentration of active component is 0.05～5mol/L, and dipping temperature is 10 DEG C～80 DEG C, and dip time is 1～24 hour；
4) silicon substrate carrier after step 3) being impregnated is dried, roasting, obtains corresponding loaded catalyst, and wherein baking temperature is 90 DEG C～150 DEG C, and drying time is 1～24 hour, and sintering temperature is 400 DEG C～650 DEG C, and roasting time is 1～24 hour.
8. it is used for the preparation method of the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation described in claim 1, it is characterised in that preparation method comprises the steps of
1) being added by silicon substrate carrier in the mixed solution of soluble salt of active component and auxiliary agent, active component concentration 0.05～5mol/L, assistant concentration is 0.05～5mol/L, and dipping temperature is 10 DEG C～80 DEG C, and dip time is 1～24 hour；
2) silicon substrate carrier after step 1) being impregnated is dried, roasting, obtains corresponding loaded catalyst, and wherein baking temperature is 90 DEG C～150 DEG C, and drying time is 1～24 hour, and sintering temperature is 400 DEG C～650 DEG C, and roasting time is 1～24 hour.
The most according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterised in that catalyst pretreatment process is to be processed 0.5～10 hour at 400 DEG C～600 DEG C in atmosphere by catalyst.
10. the catalyst described in any one of Claims 1 to 5 is for the method for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterised in that catalytic dehydrogenating reaction is with low-carbon alkanes and O2For raw material, low-carbon alkanes and O2Volume ratio is 20:1～8:1, carries out catalytic oxidative dehydrogenation and catalytic dehydrogenating reaction in the reactor, and 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, reactor is to include the one in fixed bed, fluid bed or moving bed.
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| CN105582929B (en) * | 2014-10-24 | 2018-06-08 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of low-carbon paraffin, preparation method and its usage |
| CN105582923A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst used for producing olefin through light alkane dehydrogenation |
| CN106890647B (en) * | 2015-12-17 | 2020-02-14 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene by dehydrogenating isobutane and preparation method thereof |
| CN106694017B (en) * | 2016-11-30 | 2019-10-29 | 大连理工大学 | A kind of catalyst, its optimization method and application for low-carbon alkanes oxidative dehydrogenation alkene |
| CN109289899B (en) * | 2017-07-24 | 2019-11-12 | 中国石油化工股份有限公司 | The method of composite material and preparation method and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN109939688B (en) * | 2019-04-03 | 2021-12-14 | 华东理工大学 | Iron gallium base propane dehydrogenation catalyst and preparation method thereof |
| CN113800993A (en) * | 2021-10-14 | 2021-12-17 | 中国石油化工股份有限公司 | Method and device for producing light olefins in multiple ways by coupling light alkane dehydrogenation and MTO (methanol to olefin) |
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| CN1185352A (en) * | 1996-12-19 | 1998-06-24 | 南京大学 | Catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN1185994A (en) * | 1996-12-24 | 1998-07-01 | 中国科学院兰州化学物理研究所 | Catalyst for producing isobutylene by catalytic dehydrogenation of isobutane and procedure thereof |
| CN101940922A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
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| DE602009000800D1 (en) * | 2008-07-10 | 2011-04-14 | Rohm & Haas | Autothermal catalytic hybrid process for the conversion of alkanes to alkenes and catalysts therefor |
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| CN1185352A (en) * | 1996-12-19 | 1998-06-24 | 南京大学 | Catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN1185994A (en) * | 1996-12-24 | 1998-07-01 | 中国科学院兰州化学物理研究所 | Catalyst for producing isobutylene by catalytic dehydrogenation of isobutane and procedure thereof |
| CN101940922A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
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