CN104107718A - Catalyst used for preparing olefin by dehydrating low carbon alkane, and preparation method thereof - Google Patents
Catalyst used for preparing olefin by dehydrating low carbon alkane, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst used for preparing olefin by dehydrogenating low carbon alkane, and a preparation method thereof, and mainly solves the problems of low olefin selectivity, severe carbon deposit and low one-way stability of present catalysts under high temperature conditions. The catalyst is a supported catalyst, and is prepared by adopting a dipping process with a silicon-based material as a carrier, vanadium or its oxide as an active component and iron series elements and IIIA group elements as an auxiliary agent, the catalyst catalyzes a reaction of low carbon alkane dehydrogenation to prepare olefin in an oxidation dehydrogenation and direct dehydrogenation combination mode under low O2 concentration conditions, and the catalyst is regenerated through carbon burning. The catalyst well solves the problems, and can be used in the industrial production for preparing olefin by dehydrating low carbon alkane.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for manufacturing olefin by low-carbon alkane dehydrogenation.
Background technology
Low-carbon alkene is widely used in the production of plastics, synthetic rubber, medicine, gasoline additive, ion exchange resin, washing agent, spices and various chemical intermediates, is important Organic Chemicals.Along with the development of chemical industry, very fast to the demand growth of low-carbon alkene, exploitation 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 mainly, from the steam cracking of naphtha and liquefied petroleum gas and coproduction or the by-product of refinery factory fluid catalytic cracking process, only depends on said method to be difficult to meet the demand of China's chemical industry fast development at present.Propane/dehydrogenation of isobutane technology has become propylene important after the coproduction of steam cracking and fluid catalytic cracking process or by-product/isobutene source.Industrialized propane/dehydrogenation of isobutane technique comprises the Oleflex technique of Uop Inc., the technique such as Star technique, Catofin technique, the FDB-4 of Snamprogetti SPA company and the Linde of Linde company of Air Product & Chemical company of Phillips company now.The domestic process units that still there is no dehydrogenating low-carbon alkane producing light olefins.
Dehydrogenating low-carbon alkane catalytic reaction is carried out under high temperature, low pressure condition, 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-oxide dehydrogenation is two types of direct dehydrogenations.The catalyst taking chromium element as main active component that the catalyst taking platinum element as main active component of Chinese patent (CN 96117222.3) and United States Patent (USP) (US4438288) report and Chinese patent (CN200910012450.1, CN200610126812.6) disclose is two class important catalyst of low-carbon alkanes direct dehydrogenation catalytic reaction.Low-carbon alkanes direct dehydrogenation process has realized industrial applications, but this process is subject to the restriction of thermodynamical equilibrium, has the shortcomings such as reaction temperature is high, energy consumption is large, the easily quick coking deactivation of catalyst, less stable.In recent years, the research of propane/isobutene for oxo-dehydrogenation has obtained concern, process is not subject to the restriction of thermodynamical equilibrium, but also have that catalyst activity is low, target olefine selective is poor, deep oxidation reaction is serious, accessory substance is more and product the distributes shortcoming such as restive.
In recent years, catalytic component based on vanadium has obtained research widely as the dehydrogenation of propane/iso-butane, and wherein existing oxidative dehydrogenation, also has non-oxide dehydrogenation, but still undesirable and catalyst rapid deactivation of dehydrogenation.O. Ovsitser (O. Ao Fuxisite) etc. is at " Chemical Communications " (chemical communication) 2010, " the Selective and stable iso-butene production over highly dispersed VO delivering on 46,4974 – 4976
xspecies on SiO
2supports via combining oxidative and non-oxidative iso-butane dehydrogenation " (polymolecularity VO
x/ SiO
2the isobutene for oxo-dehydrogenation of catalyst and non-oxide dehydrogenation) article reported the dehydrogenation of isobutane reaction that the oxidative dehydrogenation of barium oxide catalysis combines with non-oxide dehydrogenation, but the shortcoming of the method is that olefine selective is not high under high conversion, less stable.This research finds taking barium oxide as catalyst activity component, taking iron series element and IIIA family element as the composite assistant of composition loads on mesoporous silicon carrier, is conducive to the performance of catalyst electronic effect, thereby improves catalyst selectivity and one way stability.On the other hand, at low O
2under the aerobic conditions of content, the reaction of the mode catalysis low-carbon alkanes alkene processed combining with oxidative dehydrogenation and non-oxide direct dehydrogenation, contribute to reduce the generation of carbon deposit, make catalyst there is better activity, selective and life-span, reduce catalytic dehydrogenation processes cost.
Summary of the invention
Technical problem to be solved by this invention is that existing catalyst olefine selective under hot 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, there is while use the advantage that catalyst olefine selective is high, coking deactivation speed is slow, catalyst stability is high under hot conditions.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, is characterized in that: comprise by weight percentage following component:
A), taking silica-base material as carrier, carrier is catalyst weight 80～98.5%;
B), taking the oxide of V as active component, described active component is catalyst weight 1～10%;
C) taking the oxide of iron series element and IIIA family element as auxiliary agent, the oxide of described iron series element is catalyst weight 0.1～10%, and the oxide of described IIIA family element is catalyst weight 0.1～1.0%.
In technique scheme, the preferred version of silicon substrate carrier is the one in SBA-15, MCM-41, MCM-48 or amorphous silica, is 80～98.5% of catalyst weight; Barium oxide is catalyst activity component, is 1～10% of catalyst weight, and preferable range is 3～8%; Iron series element auxiliary agent is selected from least one in Fe, Co and Ni, and the preferable range that the oxide of iron series element accounts for catalyst weight is 0.5～5%; IIIA family element auxiliary agent is selected from least one in Ga, In and Tl, and the preferable range that the oxide of IIIA family element accounts for catalyst weight is 0.1～0.6%.
A kind of method for preparing catalyst for manufacturing olefin by low-carbon alkane dehydrogenation involved in the present invention, can adopt following steps:
1) first silicon substrate carrier is added in the soluble-salt solution of auxiliary agent, assistant concentration is 0.05～5 mol/L, and dipping temperature is 10
oc～80
oc, dip time is 1～24 hour;
2) silicon substrate carrier after step 1) dipping is dried, roasting, baking temperature is 90
oc～150
oc, be 1～24 hour drying time, sintering temperature is 400
oc～650
oc, roasting time is 1～24 hour;
3) by step 2) dipping after silicon substrate carrier join again in the soluble-salt solution of active component, the concentration of active component is 0.05～5 mol/L, dipping temperature is 10
oc～80
oc, dip time is 1～24 hour;
4) silicon substrate carrier after step 3) dipping is dried, roasting, obtain corresponding loaded catalyst, wherein baking temperature is 90
oc～150
oc, be 1～24 hour drying time, sintering temperature is 400
oc～650
oc, roasting time is 1～24 hour.
In technique scheme, immersion solvent adopts water or benzene, toluene, methyl alcohol, acetone, at least one in acetonitrile.The soluble-salt of iron series element and IIIA family element auxiliary agent can be 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 adopt following steps:
1) silicon substrate carrier is added in the mixed solution of soluble-salt of active component and auxiliary agent, active component concentration 0.05～5 mol/L, assistant concentration is 0.05～5 mol/L, dipping temperature is 10
oc～80
oc, dip time is 1～24 hour;
2) silicon substrate carrier after step 1) dipping is dried, roasting, obtain corresponding loaded catalyst, wherein baking temperature is 90
oc～150
oc, be 1～24 hour drying time, sintering temperature is 400
oc～650
oc, roasting time is 1～24 hour.
In technique scheme, immersion solvent adopts water or benzene, toluene, methyl alcohol, acetone, at least one in acetonitrile.The soluble-salt of iron series element and IIIA family element auxiliary agent can be 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 adopt and comprise following processing step:
1) catalyst pretreatment: by catalyst in air 400
oc～600
oc processes 0.5～10 hour;
2) catalytic dehydrogenation: with low-carbon alkanes and O
2for raw material, low-carbon alkanes and O
2volume ratio is 20:1～8:1, carries out catalytic oxidative dehydrogenation and catalytic dehydrogenating reaction in reactor, and reaction temperature is 400
oc～600
oc, reaction pressure is 0.08MPa～0.12MPa, alkane mass space velocity is 3.0～8.0h
-1, reactor is the one comprising in fixed bed, fluid bed or moving bed;
3) catalyst regeneration: reacted decaying catalyst carries out coke-burning regeneration, can adopt in-situ regeneration or device to regenerate outward, and regeneration temperature is 400
oc～650
oc, the recovery time is 1～10 hour, regeneration atmosphere comprises 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 N
2or at least one in Ne.Dehydrogenating propane reaction temperature is 400
oc～580
oc; Dehydrogenation of isobutane reaction temperature is 450
oc～600
oc, preferred reaction temperature is 520
oc～550
oc.
Compared with prior art, the present invention has significant advantage and high-lighting effect, and silica-base material is stronger to the adsorption capacity of active component presoma, has high-specific surface area and moderate surface acidity; Taking barium oxide as catalyst activity component, avoid the use of noble metal; The composite assistant as forming taking iron series element and IIIA family element, is conducive to the performance of catalyst electronic effect, can play good facilitation to the activity of catalyst, thereby improves catalyst selectivity and one way stability.On the other hand, at low O
2under the aerobic conditions of content, the reaction of the mode catalysis low-carbon alkanes alkene processed combining with oxidative dehydrogenation and non-oxide direct dehydrogenation, contribute to reduce the generation of carbon deposit, make catalyst there is better activity, selective and life-span, reduce catalytic dehydrogenation processes cost.
Dehydrogenating low-carbon alkane reaction is carried out on the miniature catalyst reaction device of continuous-flow quartz tube reactor.Carrier gas is He; Product analysis adopts HP-5890 gas chromatograph (HP-AL/S capillary column, 50m × 0.53mm × 15 μ m; Fid detector) alkane, olefin(e) centent in on-line analysis dehydrogenation product calculate the conversion ratio of reaction, selective and yield.The catalyst that uses method provided by the invention to prepare 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 remains on 45%, and olefine selective is higher than 90%, and catalyst performance stabilised, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
First 100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of thallous nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co oxide is catalyst weight 2.5%, the load capacity of Tl oxide is catalyst weight 0.2%.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst A.Catalyst composition is listed in table 3, and test result is listed in table 4.
[embodiment 2]
First prepare the mixed solution of ammonium metavanadate, cobalt nitrate and thallous nitrate.Then 100 g Si-MCM-41 are joined to above-mentioned solution in 80
oc dipping 2 hours, the content that makes barium oxide in catalyst is catalyst weight 5%, the load capacity of cobalt is counted 2.5% of catalyst weight with cobalt oxide, the load capacity of thallium is counted 0.2% of catalyst weight with oxide, then by the sample after dipping in baking oven 120
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst B.
[embodiment 3]
First 100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 0.05mol/L in 10
oc dipping 24 hours, in the aqueous solution of thallous nitrate 0.05mol/L in 10
oc dipping 24 hours, in catalyst, the load capacity of Co is counted 0.1% of catalyst weight with oxide, and the load capacity of Tl is counted 0.1% of catalyst weight with oxide.Then by the sample after dipping in baking oven 90
odry 24 hours of C.Dried sample again in Muffle furnace in 400
oroasting 24 hours under C.Next by the sample after roasting at 10 of the ammonium metavanadate of 0.05 mol/L
oin the C aqueous solution, flood 24 hours, to make V oxide content in catalyst be catalyst weight 1%, then by the sample after dipping in baking oven 90
odry 24 hours of C, dried sample again in Muffle furnace in 400
oroasting 24 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 400
ounder C, process 10 hours, obtain catalyst C.
[embodiment 4]
First 100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 5mol/L in 80
oc dipping 1 hour, in the aqueous solution of thallous nitrate 0.5mol/L in 80
oc dipping 1 hour, in catalyst, the load capacity of Co is counted 10% of catalyst weight with oxide, and the load capacity of Tl is counted 1.0% of catalyst weight with oxide.Then by the sample after dipping in baking oven 150
odry 1 hour of C.Dried sample again in Muffle furnace in 650
oroasting 1 hour under C.Next by the sample after roasting at 80 of the ammonium metavanadate of 0.5 mol/L
oin the C aqueous solution, flood 1 hour, to make V oxide content in catalyst be catalyst weight 10%, then by the sample after dipping in baking oven 150
odry 1 hour of C, dried sample again in Muffle furnace in 650
oroasting 2 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 600
ounder C, process 0.5 hour, obtain catalyst D.
[embodiment 5]
First prepare the mixed solution of ammonium metavanadate, cobalt nitrate and thallous nitrate.Then 100 g MCM-48 are joined to above-mentioned solution in 80
oc dipping 2 hours, make that in catalyst, barium oxide content is catalyst weight 5%, the load capacity of cobalt is counted 2.5% of catalyst weight with oxide, the load capacity of thallium is counted 0.2% of catalyst weight with oxide, then by the sample after dipping in baking oven 120
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst E.
[embodiment 6]
First 100 g SBA-15 are joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of thallous nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co is counted 2.5% of catalyst weight with oxide, and the load capacity of Tl is counted 0.2% of catalyst weight with oxide.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst F.
[embodiment 7]
First by 100 g amorphous Si
2o joins in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of thallous nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co is counted 2.5% of catalyst weight with oxide, and the load capacity of Tl is counted 0.2% of catalyst weight with oxide.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst G.
[embodiment 8]
First 100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of indium nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co is counted 2.5% of catalyst weight with oxide, and the load capacity of In is counted 0.2% of catalyst weight with oxide.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst H.
[embodiment 9]
First 100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of gallium nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co is counted 2.5% of catalyst weight with oxide, and the load capacity of Ga is counted 0.2% of catalyst weight with oxide.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst I.
[embodiment 10]
First 100 g MCM-41 are joined in the aqueous solution of nickel nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of thallium nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Ni is counted 2.5% of catalyst weight with oxide, and the load capacity of Tl is counted 0.2% of catalyst weight with oxide.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst J.
[embodiment 11]
First 100 g MCM-41 are joined in the aqueous solution of ferric nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of indium nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Fe is counted 2.5% of catalyst weight with oxide, and the load capacity of In is counted 0.2% of catalyst weight with oxide.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst K.
[embodiment 12]
First 100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of thallous nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co is counted 5.0% of catalyst weight with oxide, and the load capacity of Tl is counted 0.6% of catalyst weight with oxide.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 8.0%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst L.
[embodiment 13]
First 100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of thallous nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co is counted 0.5% of catalyst weight with oxide, and the load capacity of Tl is counted 0.1% of catalyst weight with oxide.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 3.0%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst M.
[embodiment 14]
First 100 g silica MCM-41s are joined containing in the aqueous solution of 0.5mol/L ferric nitrate, 0.5mol/L cobalt nitrate, 0.5mol/L nickel nitrate in 60
oc dipping 2 hours, then containing in the aqueous solution of 0.1mol/L gallium nitrate, 0.1mol/L indium nitrate and 0.1mol/L thallous nitrate in 60
oc dipping 2 hours, in catalyst, the oxide carried amount of Fe, Co, Ni is respectively 2.5% of catalyst weight, and the oxide carried amount of Ga, Tl, In is respectively 0.2% of catalyst weight.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst n.
[embodiment 15]
First 100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in the aqueous solution of thallous nitrate 0.1mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co oxide is catalyst weight 2.5%, the load capacity of Tl oxide is catalyst weight 0.2%.Then by the sample after dipping in baking oven 110
odry 4 hours of C.Dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, at 60 of the magnesium nitrate of 0.5 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5%, and Mg oxide content is catalyst weight 2%, then by the sample after dipping in baking oven 100
odry 4 hours of C, dried sample again in Muffle furnace in 650
oroasting 2 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 600
ounder C, process 1 hour, obtain catalyst O.
[comparative example 1]
100 g MCM-41 are joined 0.3 mol/L ammonium metavanadate 60
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5.0%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst P.
[comparative example 2]
100 g MCM-41 are joined in the aqueous solution of cobalt nitrate 0.5mol/L in 60
oc dipping 2 hours, in catalyst, the load capacity of Co is counted 2.5% of catalyst weight with oxide, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Next by the sample after roasting at 60 of the ammonium metavanadate of 0.3 mol/L
oin the C aqueous solution, flood 4 hours, to make V oxide content in catalyst be catalyst weight 5.0%, then by the sample after dipping in baking oven 110
odry 4 hours of C, dried sample again in Muffle furnace in 600
oroasting 4 hours under C.Before prepared catalyst dehydrogenation reaction, by catalyst in air 550
ounder C, process 2 hours, obtain catalyst Q.
[embodiment 16]
Catalytic reaction condition
Take 0.5g catalyst A and carry out dehydrogenation of isobutane evaluation.Alkane carrier gas is He, carries out activity rating under different temperature, pressure, condition, and test result is listed in table 1, reacts the data of 6 hours.
The dehydrogenation of isobutane catalytic condition * of table 1. catalyst A
* react iso-butane conversion ratio and the selective isobutene of 6 hours
[embodiment 17]
Take 0.5g catalyst A and carry out dehydrogenating propane evaluation.Feeding gas is propane: O
2: He=20:1:79; Temperature 550
oc; Normal pressure; Alkane mass space velocity is 4.6h
-1under condition, carry out activity rating, test result is listed in table 2.
Table 2 catalyst A catalysis dehydrogenating propane
| Reaction time (h) | Conversion of propane (%) | Propylene Selectivity (%) |
| 6 | 40.6 | 92.9 |
| 10 | 40.1 | 92.9 |
| 40 | 38.1 | 92.4 |
[embodiment 18]
Take 0.5g catalyst A～Q and carry out dehydrogenation of isobutane evaluation.Feeding gas is iso-butane: O
2: He=20:1:79; Temperature 550
oc; Normal pressure; Alkane mass space velocity is 4.6h
-1under condition, 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]
The contrast of catalyst regeneration stability
Take respectively 0.5g catalyst A, 0.5g catalyst P and 0.5g catalyst Q and carry out dehydrogenation of isobutane evaluation.Feeding gas is iso-butane: O
2: He=20:1:79; Temperature 550
oc; Normal pressure; Alkane mass space velocity is 4.6h
-1under condition, carry out catalytic dehydrogenation, charging is after 50 hours, 560
ocoke-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.
The contrast of table 5 catalyst regeneration stability
Claims (10)
1. for a catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that: comprise by weight percentage following component:
A), taking silica-base material as carrier, carrier is catalyst weight 80～98.5%;
B), taking the oxide of V as active component, described active component is catalyst weight 1～10%;
C) taking the oxide of iron series element and IIIA family element as auxiliary agent, the oxide of described iron series element is catalyst weight 0.1～10%, and the oxide of described IIIA family element is catalyst weight 0.1～1.0%.
2. according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that described low-carbon alkanes is propane or iso-butane.
3. according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that described silica-base material carrier is selected from the one in SBA-15, MCM-41, MCM-48 or amorphous silica.
4. according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that oxide taking V is as active component, described active component is catalyst weight 3～8%.
5. according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that described iron series element auxiliary agent is selected from least one in Fe, Co and Ni, the oxide of iron series element is catalyst weight 0.5～5%.
6. according to the catalyst for manufacturing olefin by low-carbon alkane dehydrogenation described in claim 1～5 any one, it is characterized in that described IIIA family element auxiliary agent is selected from least one in Ga, In and Tl, the oxide of IIIA family element is catalyst weight 0.1～0.6%.
Described in claim 1 for the preparation method of the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that preparation method comprises following steps:
1) first silicon substrate carrier is added in the soluble salt solution of auxiliary agent, 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) dipping is dried, roasting, baking temperature is 90 DEG C～150 DEG C, be 1～24 hour drying time, sintering temperature is 400 DEG C～650 DEG C, roasting time is 1～24 hour;
3) by step 2) dipping after silicon substrate carrier join again in the soluble salt solution of active component, the concentration of active component is 0.05～5mol/L, dipping temperature is 10 DEG C～80 DEG C, dip time is 1～24 hour;
4) silicon substrate carrier after step 3) dipping is dried, roasting, obtain corresponding loaded catalyst, wherein baking temperature is 90 DEG C～150 DEG C, be 1～24 hour drying time, sintering temperature is 400 DEG C～650 DEG C, roasting time is 1～24 hour.
Described in claim 1 for the preparation method of the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that preparation method comprises following steps:
1) silicon substrate carrier is added 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) dipping is dried, roasting, obtain corresponding loaded catalyst, wherein baking temperature is 90 DEG C～150 DEG C, be 1～24 hour drying time, sintering temperature is 400 DEG C～650 DEG C, roasting time is 1～24 hour.
9. according to claim 1 for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation, it is characterized in that catalyst preprocessing process for processing catalyst 0.5～10 hour at 400 DEG C～600 DEG C in air.
10. the catalyst described in claim 1～5 any one, for the method for manufacturing olefin by low-carbon alkane dehydrogenation, is characterized in that catalytic dehydrogenating reaction is with low-carbon alkanes and O
2for raw material, low-carbon alkanes and O
2volume ratio is 20:1～8:1, carries out catalytic oxidative dehydrogenation and catalytic dehydrogenating reaction in 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 the one comprising in fixed bed, fluid bed or moving bed.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105582929A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Light alkane dehydrogenation catalyst, and preparation method and application thereof |
| CN106694017A (en) * | 2016-11-30 | 2017-05-24 | 大连理工大学 | Catalyst for oxidative dehydrogenation of light alkane to prepare olefin, optimization method and application thereof |
| CN106890647A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene by dehydrogenating isobutane and preparation method thereof |
| CN109289899A (en) * | 2017-07-24 | 2019-02-01 | 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 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20100030004A1 (en) * | 2008-07-10 | 2010-02-04 | Scott Han | Hybrid autothermal catalytic process for converting alkanes to alkenes and catalysts useful for same |
| 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 |
-
2013
- 2013-04-16 CN CN201310130332.7A patent/CN104107718B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20100030004A1 (en) * | 2008-07-10 | 2010-02-04 | Scott Han | Hybrid autothermal catalytic process for converting alkanes to alkenes and catalysts useful for same |
| 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 |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105582929A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Light alkane dehydrogenation catalyst, and preparation method and application thereof |
| 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 |
| CN106890647A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene by dehydrogenating isobutane and preparation method thereof |
| 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 |
| CN106694017A (en) * | 2016-11-30 | 2017-05-24 | 大连理工大学 | Catalyst for oxidative dehydrogenation of light alkane to prepare olefin, optimization method and application 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 |
| CN109289899A (en) * | 2017-07-24 | 2019-02-01 | 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 |
| 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 |
| CN109939688A (en) * | 2019-04-03 | 2019-06-28 | 华东理工大学 | Iron gallium base propane dehydrogenation catalyst and preparation method thereof |
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