CN104549415B - Catalyst and its application method for manufacturing olefin by low-carbon alkane dehydrogenation - Google Patents
Catalyst and its application method for manufacturing olefin by low-carbon alkane dehydrogenation Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst and its application method for manufacturing olefin by low-carbon alkane dehydrogenation, mainly solve to be currently used for the problem of low manufacturing olefin by low-carbon alkane dehydrogenation vanadium oxide catalysts decentralization in high capacity amount, the easy accumulative crystallization of active component, catalytic activity are relatively low, target alkene selectivity is not high.The present invention passes through a kind of catalyst of use manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof and process, the catalyst is using silica-base material as carrier, using vanadium or its oxide as active component, active component is loaded using the method for synthesis, using rare earth oxide and Group IIIA element oxide as auxiliary agent, auxiliary agent is loaded using the method for dipping, using more gentle CO2The reaction of preparing isobutene through dehydrogenation of iso-butane is realized as oxidant, the technical scheme of Burning Coke on Catalyst regeneration is finally carried out, the problem is preferably solved, in the industrial production available for dehydrogenation of isobutane producing light olefins.
Description
Technical field
The present invention relates to a kind of catalyst and its application method for manufacturing olefin by low-carbon alkane dehydrogenation.
Background technology
Dehydrating alkanes are to significant effectively using fossil resources.At present, a large amount of lower alkanes obtained by oil plant
Hydrocarbon is the main component of liquefied petroleum gas, is mainly used as domestic fuel, is underutilized, and added value is very low, utilizes low-carbon
Dehydrating alkanes produce low-carbon alkene, there is huge application prospect.Low-carbon alkene is a kind of important Organic Chemicals, extensively
Applied to medicine, plastics, synthetic rubber, gasoline additive, ion exchange resin, detergent, spices and various chemical intermediates
Production.With the development of chemical industry, to the demand growth of low-carbon alkene quickly, exploitation is produced by the low carbon alkane of added value
Low carbon olefin hydrocarbon is for making full use of low-carbon alkanes resource, to open up new alkene source significant.Propylene/isobutene
Essentially from coproduction or the by-product of the steam cracking and refinery factory fluid catalytic cracking process of naphtha and liquefied petroleum gas, at present
Only it has been difficult to meet the fast-developing demand of China's chemical industry by the above method.Propane/dehydrogenation of isobutane technology has become
Important propylene/isobutene source after the coproduction of steam cracking and fluid catalytic cracking process or by-product.Propane/iso-butane
Dehydrogenation has been industrialized now, the main Oleflex techniques including Uop Inc., the Star techniques of Phillips companies, Air
The Catofin techniques of Product ＆ Chemical companies, FDB-4 the and Linde companies of Snamprogetti SPA companies
The techniques such as Linde.
Dehydrogenating low-carbon alkane catalytic reaction is carried out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, and exploitation is high living
Property, high selectivity and high stability and lower-cost catalyst turns into the key of the technology.Current industrialized catalyst
Mainly have two classes, a class using metal oxide as active component, such as Chinese patent (CN200910012450.1,
CN200610126812.6) the catalyst using chromium as main active component disclosed, active high, cost is more low excellent
Point, but inactivation is fast, and it is poisonous, be difficult to meet environmental requirement.Another kind of is loaded noble metal catalyst, such as Chinese patent
(CN96117222.3, CN101380587A) and United States Patent (USP) (US4438288) report using platinum element as main active component
Catalyst, has the advantages that stability is preferable, but expensive, and activity and selectivity still needs to further raising.
Catalyst for dehydrogenation of low-carbon paraffin can be divided into oxidative dehydrogenation and direct dehydrogenation two types.Direct dehydrogenation process by
The limitation of thermodynamical equilibrium, have that reaction temperature is high, energy consumption is big, catalyst easily quick coking deactivation, less stable the shortcomings of.
Because of the intrinsic problem of direct dehydrogenation, researcher has developed O2Or CO2As the oxidative dehydrogenation of oxidant, low-carbon alkanes oxidation is de-
Hydrogen is not limited by thermodynamical equilibrium, but O2Low-carbon alkanes oxidative dehydrogenation under atmosphere there is also target alkene it is selectively poor,
The shortcomings of deep oxidation reaction is serious, accessory substance is more and product distribution is difficult to control.And as more gentle oxidant,
CO2Catalysis oxidation dehydrogenating low-carbon alkane in atmosphere is also studied, and Chinese patent (CN102000598B) is reported with vanadium
Oxide is active component, the catalyst using mesopore molecular sieve MSU-1 as carrier is in CO2The catalytic of dehydrogenation of isobutane in atmosphere
Can, both promote CO2Recycling, the stability of catalyst is improved again, but in higher alkane conversion, target alkene
Hydrocarbon-selective is still not ideal enough relative to industrializeding catalyst, and when iso-butane conversion ratio is 38.4%, selective isobutene is
83.2%。
In the document report that vanadium series catalyst is used for dehydrogenation of isobutane, Yinghuan Fu etc. are in Journal of
Molecular Catalysis A:" the Characterization and delivered on Chemical 221 (2004) 163-168
reactivity of SnO2-doped V2O5/γ-Al2O3 catalysts in dehydrogenation of
Isobutane to isobutene " articles use 3wt%SnO2-10wt%V2O5/Al2O3Catalyst has 44.5% iso-butane
Conversion ratio and 92.3% selective isobutene (table 1), this, which is that vanadium series catalyst is optimal in dehydrogenation of isobutane document report, comments
Valence mumber evidence.
The study find that using the barium oxide of high dispersive as catalyst activity component, with rare earth oxide and IIIA
Race's element oxide is supported on mesoporous silica-base material carrier for the composite assistant of composition, under the process conditions of optimization, vanadium base
Catalyst, which is used for manufacturing olefin by low-carbon alkane dehydrogenation, has preferably activity, selectivity and stability, reduction catalytic dehydrogenation processes into
This.
The content of the invention
Present invention mainly solves exist present in prior art for manufacturing olefin by low-carbon alkane dehydrogenation vanadium oxide catalysts
Decentralization is low during high capacity amount, the easy accumulative crystallization of active component, the problem of catalytic activity is relatively low, target alkene selectivity is not high,
A kind of new catalyst for manufacturing olefin by low-carbon alkane dehydrogenation is provided, the method for preparing catalyst is easy, and active component is disperseed
Degree is high, optimization of process conditions, with the high temperature conditions in use, catalyst carbon deposit deactivation rate is slow, catalyst stability is high,
Target alkene selectively high advantage.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is used for dehydrogenating low-carbon alkane system
The catalyst of alkene, by weight percentage comprising following components：
A) using silica-base material as carrier, carrier is the 79~98.8% of catalyst weight；
B) using V oxides as active component, active component is the 1~10% of catalyst weight；
C) using the oxide of rare earth element as auxiliary agent, the rare earth oxide is the 0.1~10% of catalyst weight；
D) oxide using IIIA races element is auxiliary agent, and IIIA races element oxide is the 0.1 of catalyst weight
~1.0%.
In above-mentioned technical proposal, the low-carbon alkanes are propane or iso-butane；Silicon substrate carrier is selected from SBA-15, MCM-41
Or one kind in MCM-48, it is the 90~99% of catalyst weight；Barium oxide is catalyst activity component, and content is catalyst
The 1~10% of weight, content preferred scope is the 2~8% of catalyst weight；Rare earth oxide auxiliary agent in La and Ce at least
One kind, is the 0.1~10% of catalyst weight, and the preferred scope that rare earth oxide accounts for catalyst weight is 0.5~5%；IIIA races
At least one of the element auxiliary agent in Ga or In, the oxide content of IIIA races element for catalyst weight 0.1~
1.0%, content preferred scope is the 0.1~0.8% of catalyst weight.
Preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation involved in the present invention, catalyst activity component V
The oxide carried synthesis preparation method to carrier is comprised the steps of：
1) V2O5The alkoxide compound V (OR) of vanadium is obtained through being reacted shown in I formula with fatty alcohol3O：
Ⅰ
In formula, R is methyl, ethyl, propyl group, butyl, the tert-butyl group or isopropyl, and reaction dissolvent is toluene or benzene, reaction temperature
Spend for 60 oC~120 oC, the reaction time is 10~48 hours, and V is isolated after the completion of reaction2O5, remove solvent, moisture and alcohol
Afterwards, the alkoxide compound crystal of vanadium is obtained, 90 oC~150 oDried 1~24 hour under C；
2）By the alkoxide compound V (OR) of vanadium3O is dissolved at least one organic solvent in toluene, benzene, acetone or ether
In, then it is impregnated on silicon substrate carrier, wherein dipping temperature is 10 oC~60 oC, dip time is 1~24 hour, the alkane of vanadium
Oxo-compound V (OR)3O occurs after being reacted shown in II formula with silicon substrate carrier surface hydroxyl, and through drying and being calcined, drying temperature is
90 oC~150 oC, drying time is 1~24 hour, and sintering temperature is 400 oC~650 oC, roasting time is 1~24 hour,
Produce corresponding supported vanadium-based catalyst.
Ⅱ
In formula, R is methyl, ethyl, propyl group, butyl, the tert-butyl group or isopropyl.
In above-mentioned technical proposal, step 1) V2O5Reaction with fatty alcohol is in N2Or carried out under the inert gas shielding such as Ar；
The alkoxide compound V (OR) of vanadium3In O, R is one kind in methyl, ethyl, propyl group, butyl, the tert-butyl group or isopropyl, preferably
Scheme is one kind in the tert-butyl group or isopropyl.
In above-mentioned technical proposal, step 2）At least one of the organic solvent in toluene, benzene, acetone or ether, preferably
Scheme is one kind in toluene or ether.
Preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation involved in the present invention, catalyst promoter component is dilute
The impregnation preparation method that earth elements oxide and IIIA races element oxide load to carrier can be using comprising the steps of：
1) the medium volume impregnation of soluble salt solution for silicon substrate carrier being firstly added into rare earth element, dipping temperature is 10 oC
~80 oC, dip time is 1~24 hour；
2）By step 1）Silicon substrate carrier after dipping is dried, is calcined, and drying temperature is 90 oC~150 oC, when drying
Between be 1~24 hour, sintering temperature is 400 oC~650 oC, roasting time is 1~24 hour；
3) by step 2）Silicon substrate carrier after dipping is then added to the medium volume leaching of soluble salt solution of IIIA races element
Stain, dipping temperature is 10 oC~80 oC, dip time is 1~24 hour；
4）By step 3）Silicon substrate carrier after dipping is dried, is calcined, and produces corresponding loaded catalyst, wherein dry
Dry temperature is 90 oC~150 oC, drying time is 1~24 hour, and sintering temperature is 400 oC~650 oC, roasting time be 1~
24 hours.
In above-mentioned technical proposal, immersion solvent uses at least one in water or methanol, ethanol, acetone, and preferred scheme is
The soluble-salt of one kind in water or ethanol, rare earth element and IIIA races element auxiliary agent may be selected from chloride, nitrate or acetic acid
One kind in salt.
Another rare earth oxide and IIIA race element oxide adjuvant component loads to the dipping preparation side of carrier
Method, can use following steps：
1) silicon substrate carrier is added to the medium volume impregnation of mixed solution of the soluble salt of rare earth element and IIIA races element,
Dipping temperature is 10 oC~80 oC, dip time is 1~24 hour；
2）By step 1）Silicon substrate carrier after dipping is dried, is calcined, and produces corresponding loaded catalyst, wherein dry
Dry temperature is 90 oC~150 oC, drying time is 1~24 hour, and sintering temperature is 400 oC~650 oC, roasting time be 1~
24 hours.
In above-mentioned technical proposal, immersion solvent uses at least one in water or methanol, ethanol, acetone, and preferred scheme is
The soluble-salt of one kind in water or ethanol, rare earth element and IIIA races element auxiliary agent may be selected from chloride, nitrate or acetic acid
One kind in salt.
The application of catalyst involved in the present invention in manufacturing olefin by low-carbon alkane dehydrogenation, can be used comprising following technique step
Suddenly：
1) catalyst is pre-processed：By catalyst in CO2400 in atmosphereoC~600 oC is handled 1~10 hour；
2) catalytic dehydrogenation：With iso-butane and CO2For raw material, iso-butane and CO2Volume ratio is 1：1~1：10, reaction temperature
For 400oC~600 oC, reaction pressure is 0.08MPa~0.15MPa, and the mass space velocity of iso-butane is 4.0~10.0h-1；
3) catalyst regenerates：Reacted decaying catalyst carries out CO2Coke-burning regeneration, can be used outside in-situ regeneration or device
Regeneration, regeneration temperature is 400oC~650 oC, the recovery time is 1~10 hour.
In above-mentioned technical proposal, iso-butane and CO2Volume ratio is 1：1~1：10, volume ratio preferred scheme is 1：1~1：5.
For CO2The catalytic activity of oxidation dehydrogenation of isobutane alkene catalytic component based on vanadium depends primarily on its catalyst knot
Structure, the decentralization of vanadium active component, the property and process of catalyst carrier.Compared with prior art, the present invention has
Significant advantage and high-lighting effect, using barium oxide as catalyst activity component, it is to avoid the use of noble metal；Silica-base material
The catalyst that mesopore molecular sieve is prepared as carrier has uniform pore-size distribution, higher specific surface area, to active component
Bearing capacity is stronger, and with suitable surface acidity；Active component vanadium is loaded on carrier in the method for synthesis, significantly carried
The dispersiveness and catalyst stability of high active component barium oxide；With rare earth oxide and IIIA races element oxide
Thing is the composite assistant of composition, and the catalysis dehydrogenation performance to catalyst can play good facilitation, appropriate auxiliary agent tool
There is scattered, isolation active component barium oxide, it will be apparent that the decentralization of active component is improved, while also making catalyst
With more preferable anti-carbon deposition ability；Using more gentle CO2As oxidant, under the process conditions of optimization, CO is promoted2
Recycling, catalyst also has preferably activity, selectivity and stability, reduces catalytic dehydrogenation processes cost.
Dehydrogenating low-carbon alkane reaction is carried out on the continuously flowing miniature catalyst reaction device of quartz tube reactor.Product analysis
Using HP-5890 gas chromatographs (HP-AL/S capillary columns, 50m × 0.53mm × 15 μm；Fid detector) on-line analysis take off
Alkane, olefin(e) centent in hydrogen product and conversion ratio, selectivity and the yield for calculating reaction.The method provided using the present invention
The catalyst of preparation reacts for dehydrogenation of isobutane, and iso-butane conversion ratio reaches close to 40%, olefine selective or close to 90%；Through
Coke-burning regeneration is crossed, catalyst performance keeps stable, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
By 40g V2O5It is added to the 400mL tert-butyl alcohols in 1.2L toluene, 110o24h is reacted under C, course of reaction is produced
Water separated with water knockout drum, with V2O5Dissolving, solution is changed into red from faint yellow, will be unreacted after the completion of reaction
V2O5It is filtered to remove, then depressurizes and steam toluene and the tert-butyl alcohol, obtains V (OC (CH3)3)3O white crystals, the product is again 100 oC
Lower vacuum drying 12 hours.
Under Ar protections, by the V (OC (CH prepared by 12.45g3)3)3O and 92.5g pure silicon molecular sieves MCM-41 is added
Into 300mL toluene, 60oImpregnate 1 hour, then steam toluene decompression under C, then 120 oIt is dry 2 hours under C, finally
600 oIt is calcined 4 hours under C, active component barium oxide is the 5% of catalyst weight.
Products obtained therefrom is added to 6.23g lanthanum nitrates（La(NO3)3·6H2O）The aqueous solution in 60 oC incipient impregnations 2
Hour, the load capacity of La oxides is 2 % of catalyst weight in catalyst.Then by the sample after dipping in an oven 110oC is dried 4 hours.Dried sample is again in Muffle furnace in 600 oIt is calcined 4 hours under C.Catalyst is then added to 1.08g nitre
In 60 in the aqueous solution of sour indium oC incipient impregnations 2 hours, the load capacity of In oxides is catalyst weight in catalyst
0.5%.Then by the sample after dipping in an oven 110 oC is dried 4 hours.Dried sample is again in Muffle furnace in 600oIt is calcined 4 hours under C, produces corresponding supported vanadium-based catalyst.Before prepared catalyst dehydrogenation reaction, it will urge
Agent is in CO2550 in atmosphere oHandled 2 hours under C, obtain catalyst A.
【Embodiment 2】
By 40g V2O5It is added to the 400mL tert-butyl alcohols in 1.2L toluene, 110o24h is reacted under C, course of reaction is produced
Water separated with water knockout drum, with V2O5Dissolving, solution is changed into red from faint yellow, will be unreacted after the completion of reaction
V2O5It is filtered to remove, then depressurizes and steam toluene and the tert-butyl alcohol, obtains V (OC (CH3)3)3O white crystals, the product is again 100 oC
Lower vacuum drying 12 hours.Under Ar protections, by the V (OC (CH prepared by 12.45g3)3)3O and 92.5g pure silicon molecular sieves
MCM-41 is added in 300mL toluene, 60oImpregnate 1 hour, then steam toluene decompression under C, then 120 o2 are dried under C
Hour, finally 600 oIt is calcined 4 hours under C, active component barium oxide is the 5% of catalyst weight.
Prepare 6.23g lanthanum nitrates（La(NO3)3·6H2O) and 1.08g indium nitrates mixed aqueous solution, by above-mentioned load vanadium
The product of oxide is added in the aqueous solution in 60 oC incipient impregnations 2 hours, then by the sample after dipping in an oven 110oC is dried 4 hours, and dried sample is again in Muffle furnace in 600 oIt is calcined 4 hours under C, the load of La oxides in catalyst
2 % for catalyst weight are measured, the load capacity of In oxides is the 0.5% of catalyst weight.Corresponding load-type vanadium base is produced to urge
Agent.Before prepared catalyst dehydrogenation reaction, by catalyst in CO2550 in atmosphere oHandle 2 hours, obtain under C
To catalyst B.
【Embodiment 3】
By 40g V2O5It is added to the 400mL tert-butyl alcohols in 1.2L toluene, 60o48h is reacted under C, what course of reaction was produced
Water is separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then decompression steams toluene and the tert-butyl alcohol, obtains V
(OC(CH3)3)3O white crystals, the product is again 90 oIt is dried in vacuo 24 hours under C.In N2Under protection, by prepared by 2.49g
V (OC (CH3)3)3O and 98.8g pure silicon molecular sieves MCM-41 is added in 300mL acetone, 10 oDipping 24 hours under C, so
Acetone decompression is steamed afterwards, then 90 oDried 24 hours under C, finally 400 oIt is calcined 24 hours under C, the oxidation of active component vanadium
Thing is the 1% of catalyst weight.
Products obtained therefrom is added to 0.3g lanthanum nitrates（La(NO3)3·6H2O）The aqueous solution in 10oC incipient impregnations 24
Hour, then by the sample after dipping in an oven 90 oC is dried 24 hours.Dried sample is again in Muffle furnace in 400oIt is calcined 24 hours under C, the load capacity of La oxides is the 0.1% of catalyst weight in catalyst.Catalyst is then added to
In 10 in the aqueous solution of 0.216g indium nitrates oC incipient impregnations 24 hours, then by the sample after dipping in an oven 90 oC
Dry 24 hours, dried sample is again in Muffle furnace in 400 oIt is calcined 24 hours under C, In load capacity is with oxygen in catalyst
Compound is calculated as the 0.1% of catalyst weight.Produce corresponding supported vanadium-based catalyst.In prepared catalyst dehydrogenation
Before reaction, by catalyst in CO2400 in atmosphere oHandled 10 hours under C, obtain catalyst C.
【Embodiment 4】
By 40g V2O5It is added to the 400mL tert-butyl alcohols in 1.2L toluene, 120o10h is reacted under C, course of reaction is produced
Water separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then decompression steams solvent and the tert-butyl alcohol, obtains
To V (OC (CH3)3)3O white crystals, the product is again 150 oIt is dried in vacuo 1 hour under C.Under Ar protections, by 24.90g institutes
V (OC (the CH of preparation3)3)3O and 79g pure silicon molecular sieves MCM-41 is added in 300mL benzene, 60oDipping 1 hour under C, so
Benzene decompression is steamed afterwards, then 150 oDried 1 hour under C, finally 650 oIt is calcined 1 hour under C, active component barium oxide
For the 10% of catalyst weight.
Products obtained therefrom is added to 31.15g lanthanum nitrates（La(NO3)3·6H2O）The aqueous solution in 80oC incipient impregnations
1 hour, La load capacity was calculated as the 10% of catalyst weight with oxide in catalyst, then by the sample after dipping in baking oven
In 150 oC is dried 1 hour.Dried sample is again in Muffle furnace in 650 oIt is calcined 1 hour under C.Catalyst is then added to
In 80 in the aqueous solution of 2.16g indium nitrates oC incipient impregnations 1 hour, In load capacity is calculated as catalysis with oxide in catalyst
The 1.0% of agent weight.Then by the sample after dipping in an oven 150 oC is dried 1 hour.Dried sample is again in Muffle furnace
In in 650 oIt is calcined 1 hour under C, produces corresponding supported vanadium-based catalyst.In prepared catalyst dehydrogenation reaction
Before, by catalyst in CO2600 in atmosphere oHandled 1 hour under C, obtain catalyst D.
【Embodiment 5】
By 40g V2O5It is added to the 400mL tert-butyl alcohols in 1.2L ether, 60o24h is reacted under C, what course of reaction was produced
Water is separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then depressurizes and steam toluene and the tert-butyl alcohol, obtains V
(OC(CH3)3)3O white crystals, the product is again 100 oIt is dried in vacuo 12 hours under C.Under Ar protections, by prepared by 4.25g
V (OC (CH3)3)3O and 97.4g pure silicon molecular sieves MCM-41 is added in 300mL ether, 10oDipping 12 hours under C, so
Solvent under reduced pressure is steamed afterwards, then 120 oDried 2 hours under C, finally 600 oIt is calcined 5 hours under C, the oxidation of active component vanadium
Thing is the 2% of catalyst weight.
Products obtained therefrom is added to 1.56g lanthanum nitrates（La(NO3)3·6H2O）Methanol/acetone mixed solution (methanol
With acetone volume ratio=1:1) in 80 inoC incipient impregnations 2 hours, La load capacity is calculated as catalysis with oxide in catalyst
The 0.5% of agent weight, then by the sample after dipping in an oven 120 oC is dried 4 hours.Dried sample is again in Muffle furnace
In in 600 oIt is calcined 4 hours under C, catalyst is then added to methanol/acetone mixed solution (methanol and the acetone of 0.216g indium nitrates
Volume ratio=1:1) in 80 in solution oC incipient impregnations 2 hours, In load capacity is calculated as catalyst with oxide in catalyst
The 0.1% of weight.Then by the sample after dipping in an oven 120 oC is dried 4 hours.Dried sample is again in Muffle furnace
In 600 oIt is calcined 4 hours under C, produces corresponding supported vanadium-based catalyst.Before prepared catalyst dehydrogenation reaction,
By catalyst in CO2550 in atmosphere oHandled 2 hours under C, obtain catalyst E.
【Embodiment 6】
By 20g V2O5It is added to 200mL isopropanols in 0.6L benzene, 70o48h, the water that course of reaction is produced are reacted under C
Separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then depressurizes and steam benzene and alcohol, obtains V (OCH
(CH3)2)3O white crystals, the product is again 90oIt is dried in vacuo 24 hours under C.In N2Under protection, by the V prepared by 17.0g
(OCH(CH3)2)3O and 86.2g pure silicon molecular sieves MCM-41 is added in the mixed solvent of 300mL acetone and ether (acetone and second
The volume ratio of ether is 1:1), 40oImpregnate 6 hours, then steam solvent under reduced pressure under C, then 90oIt is dry 24 hours under C, most
Afterwards 500 oIt is calcined 24 hours under C, active component barium oxide (VO4 3-) it is the 8% of catalyst weight.
Products obtained therefrom is added to 15.6g lanthanum nitrates（La(NO3)3·6H2O）Ethanol solution in 80oC soaks in equal volume
Stain 1 hour, La load capacity is calculated as the 5% of catalyst weight with oxide in catalyst, then by the sample after dipping in baking oven
In 110 oC is dried 4 hours.Dried sample is again in Muffle furnace in 600 oIt is calcined 4 hours under C, catalyst is then added to
In 80 in the ethanol solution of 1.73g indium nitratesoC incipient impregnations 1 hour, In load capacity is calculated as urging with oxide in catalyst
The 0.8% of agent weight, then by the sample after dipping in an oven 110 oC is dried 4 hours.Dried sample is again in Muffle
In 600 in stove oIt is calcined 4 hours under C, produces corresponding supported vanadium-based catalyst.It is anti-in prepared catalyst dehydrogenation
Ying Qian, by catalyst in CO2500 in atmosphere oHandled 6 hours under C, obtain catalyst F.
【Embodiment 7】
By 20g V2O5It is added to 200mL isopropanols in 0.6L toluene, 120o10h is reacted under C, course of reaction is produced
Water separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then decompression steams toluene and isopropanol, obtains
To V (OCH (CH3)2)3O white crystals, the product is again 120oIt is dried in vacuo 2 hours under C.In N2Under protection, by 10.63g institutes
V (OCH (the CH of preparation3)2)3O and 92.4g pure silicon molecular sieves MCM-41 is added in 300mL ether, 40oDipping 8 is small under C
When, then solvent under reduced pressure is steamed, then 120oDried 2 hours under C, finally 650 oIt is calcined 2 hours under C, active component vanadium
Oxide is the 5% of catalyst weight.
Prepare 5.29g cerous nitrates（Ce(NO3)3·6H2O), 1.36g gallium nitrates and 0.64g magnesium nitrates (Mg (NO3)2·
6H2O mixed aqueous solution), the product of above-mentioned load barium oxide is added in the aqueous solution in 60 oC incipient impregnations 2 are small
When, then by the sample after dipping in an oven 110 oC is dried 4 hours, and dried sample is again in Muffle furnace in 600 oC
Lower roasting 4 hours, the load capacity of Ce oxides is that the load capacity of 2%, the Ga oxides of catalyst weight is catalyst in catalyst
The load capacity of 0.5%, the Mg oxides of weight is the 0.1% of catalyst weight.Produce corresponding supported vanadium-based catalyst.Institute
Before the catalyst dehydrogenation reaction of preparation, by catalyst in CO2600 in atmosphere oHandled 1 hour under C, obtain catalyst G.
【Embodiment 8】
By 30g V2O5It is added to 300mL propyl alcohol in 0.9L toluene, 110o12h is reacted under C, what course of reaction was produced
Water is separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then decompression steams toluene and propyl alcohol, obtains V
(OCH2CH2CH3)3O white crystals, the product exists again, and 120oIt is dried in vacuo 6 hours under C.In N2It is under protection, 10.63g is made
Standby V (OCH2CH2CH3)3O and 92.5g pure silicon molecular sieves MCM-41 is added in 300mL acetone, 30oImpregnated 8 hours under C,
Then solvent under reduced pressure is steamed, then 120oDried 6 hours under C, finally 600 oIt is calcined 4 hours under C, the oxidation of active component vanadium
Thing is the 5% of catalyst weight.
Prepare 5.29g cerous nitrates（Ce(NO3)3·6H2O) and 1.08g indium nitrates mixed aqueous solution, by above-mentioned load vanadium
The product of oxide is added in the aqueous solution in 40 oC incipient impregnations 4 hours, then by the sample after dipping in an oven 110oC is dried 4 hours, and dried sample is again in Muffle furnace in 600 oIt is calcined 4 hours under C, the load of Ce oxides in catalyst
The load capacity for measuring 2%, the In oxides for catalyst weight is the 0.5% of catalyst weight.Corresponding load-type vanadium base is obtained to urge
Agent.Before prepared catalyst dehydrogenation reaction, by catalyst in CO2550 in atmosphere oHandle 2 hours, obtain under C
To catalyst H.
【Embodiment 9】
By 40g V2O5It is added to 400mL butanol in 1.2L toluene, 110o24h is reacted under C, what course of reaction was produced
Water is separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then depressurizes and steam toluene and the tert-butyl alcohol, obtains V
(OCH2CH2CH2CH3)3O, the product is again 100 oIt is dried in vacuo 12 hours under C.Under Ar protections, by prepared by 12.45g
V(OCH2CH2CH2CH3)3O and 92.5g pure silicon molecular sieves MCM-41 is added in 300mL toluene, 60oDipping 1 hour under C, so
Solvent under reduced pressure is steamed afterwards, then 120 oDried 2 hours under C, finally 600 oIt is calcined 4 hours under C, the oxidation of active component vanadium
Thing is the 5% of catalyst weight.
Prepare 6.23g lanthanum nitrates（La(NO3)3·6H2O) and 1.36g gallium nitrates mixed aqueous solution, by above-mentioned load vanadium
The product of oxide is added in the aqueous solution in 40 oC incipient impregnations 4 hours, then by the sample after dipping in an oven 110oC is dried 4 hours, and dried sample is again in Muffle furnace in 600 oIt is calcined 4 hours under C, the load of La oxides in catalyst
The load capacity for measuring 2%, the Ga oxides for catalyst weight is the 0.5% of catalyst weight.Corresponding load-type vanadium base is obtained to urge
Agent.Before prepared catalyst dehydrogenation reaction, by catalyst in CO2550 in atmosphere oHandle 2 hours, obtain under C
To catalyst I.
【Embodiment 10】
By 40g V2O5It is added to the 400mL tert-butyl alcohols in 1.2L toluene, 110o24h is reacted under C, course of reaction is produced
Water separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then depressurizes and steam toluene and the tert-butyl alcohol, obtains V
(OC(CH3)3)3O, the product is again 100 oIt is dried in vacuo 12 hours under C.Under Ar protections, by the V (OC prepared by 12.45g
(CH3)3)3O is added in 300mL toluene with 92.5g pure silicon MCM-48 molecular sieves, 60oImpregnated 1 hour under C, then by first
Benzene decompression is steamed, then 120 oDried 2 hours under C, finally 600 oIt is calcined 4 hours under C, active component barium oxide is to urge
The 5% of agent weight.
The mixed aqueous solution of 3.01g lanthanum chlorides and 0.8g inidum chlorides is prepared, the product of above-mentioned load barium oxide is added
In 40 in the aqueous solution oC incipient impregnations 4 hours, then by the sample after dipping in an oven 110 oC is dried 4 hours, is done
Sample after dry is again in Muffle furnace in 600 oIt is calcined 4 hours under C, the load capacity of La oxides is catalyst weight in catalyst
2%, In oxides load capacity be catalyst weight 0.5%.Obtain corresponding supported vanadium-based catalyst.Prepared
Before catalyst dehydrogenation reaction, by catalyst in CO2550 in atmosphere oHandled 2 hours under C, obtain catalyst J.
【Embodiment 11】
By 40g V2O5It is added to the 400mL tert-butyl alcohols in 1.2L toluene, 110o24h is reacted under C, course of reaction is produced
Water separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then depressurizes and steam toluene and the tert-butyl alcohol, obtains V
(OC(CH3)3)3O, the product is again 100 oIt is dried in vacuo 12 hours under C.Under Ar protections, by the V (OC prepared by 12.45g
(CH3)3)3O is added in 300mL toluene with 92.5g SBA-15 molecular sieves, 60oImpregnate 2 hours, then subtract toluene under C
Pressure is steamed, then 120 oDried 2 hours under C, finally 600 oIt is calcined 4 hours under C, active component barium oxide is catalyst
The 5% of weight.
The mixed aqueous solution of 3.88g lanthanum acetates and 1.05g indium acetates is prepared, the product of above-mentioned load barium oxide is added
In 40 in the aqueous solution oC incipient impregnations 4 hours, then by the sample after dipping in an oven 110 oC is dried 4 hours, is done
Sample after dry is again in Muffle furnace in 600 oIt is calcined 4 hours under C, the load capacity of La oxides is catalyst weight in catalyst
2%, In oxides load capacity be catalyst weight 0.5%.Obtain corresponding supported vanadium-based catalyst.Prepared
Before catalyst dehydrogenation reaction, by catalyst in CO2550 in atmosphere oHandled 2 hours under C, obtain catalyst K.
【Embodiment 12】
By 40g V2O5It is added to the 400mL tert-butyl alcohols in 1.2L toluene, 110o24h is reacted under C, course of reaction is produced
Water separated with water knockout drum, by unreacted V after the completion of reaction2O5It is filtered to remove, then depressurizes and steam toluene and the tert-butyl alcohol, obtains V
(OC(CH3)3)3O white crystals, the product is again 100 oIt is dried in vacuo 12 hours under C.Under Ar protections, by prepared by 12.45g
V (OC (CH3)3)3O and 92.5g pure silicon molecular sieves MCM-41 is added in 300mL toluene, 40oDipping 12 hours under C, so
Toluene decompression is steamed afterwards, then 120 oDried 2 hours under C, then 600 oIt is calcined 4 hours under C, the oxidation of active component vanadium
Thing is the 5% of catalyst weight.
Prepare 2.65g cerous nitrates（Ce(NO3)3·6H2O), 3.12g lanthanum nitrates（La(NO3)3·6H2O), 0.68g gallium nitrates
With the mixed aqueous solution of 0.54g indium nitrates, the product of above-mentioned load barium oxide is added in the aqueous solution in 40 oC is isometric
Dipping 4 hours, then by the sample after dipping in an oven 110 oC dry 4 hours, dried sample again in Muffle furnace in
600 oIt is calcined 4 hours under C, the load capacity of Ce oxides is for the load capacity of 1%, the La oxides of catalyst weight in catalyst
The load capacity of 1%, the Ga oxides of catalyst weight is that the load capacity of 0.25%, the In oxides of catalyst weight is catalyst weight
The 0.25% of amount.Obtain corresponding supported vanadium-based catalyst.Before prepared catalyst dehydrogenation reaction, by catalyst
In CO2550 in atmosphere oHandled 2 hours under C, obtain catalyst L.
【Comparative example 1】
By 95 g SiO2In the aqueous solution for being added to 6.43g ammonium metavanadates, 60oImpregnated under C 1 hour, then will dipping
Sample afterwards in an oven 120 oDried 2 hours under C, dried sample is again in Muffle furnace in 600 oIt is calcined 4 hours under C,
V in catalyst2O5Content is the 5.0% of catalyst weight.Before catalyst dehydrogenation reaction prepared by infusion process, it will be catalyzed
Agent is in CO2550 in atmosphere oHandled 2 hours under C, obtain catalyst M.
【Comparative example 2】
Under Ar protections, by 12.45g V (OCH2CH2CH2CH3)3O and 93.0g pure silicon molecular sieves MCM-41 is added to
In 300mL toluene, 60oImpregnate 1 hour, then steam solvent under reduced pressure under C, then 120 oDry 2 hours, finally exist under C
600 oIt is calcined 4 hours under C, active component barium oxide is the 5% of catalyst weight.
Prepare 6.23g lanthanum nitrates（La(NO3)3·6H2O the aqueous solution), the product of above-mentioned load barium oxide is added should
In 40 in the aqueous solution oC incipient impregnations 4 hours, then by the sample after dipping in an oven 110 oC is dried 4 hours, is dried
Sample afterwards is again in Muffle furnace in 600 oIt is calcined 4 hours under C, the load capacity of La oxides is catalyst weight in catalyst
2%, obtain corresponding supported vanadium-based catalyst.Before prepared catalyst dehydrogenation reaction, by catalyst in CO2Gas
550 in atmosphere oHandled 2 hours under C, obtain catalyst n.
【Comparative example 3】
Under Ar protections, by the V (OCH prepared by 12.45g2CH2CH2CH3)3O and 94.5g pure silicon molecular sieves MCM-41 adds
Enter into 300mL toluene, 60oImpregnate 1 hour, then steam solvent under reduced pressure under C, then 120 oIt is dry 2 hours under C, most
Afterwards 600 oIt is calcined 4 hours under C, active component barium oxide is the 5% of catalyst weight.
The aqueous solution of 1.36g gallium nitrates is prepared, the product of above-mentioned load barium oxide is added in the aqueous solution in 40 oC
Incipient impregnation 4 hours, then by the sample after dipping in an oven 110 oC is dried 4 hours, and dried sample is again in Muffle
In 600 in stove oIt is calcined 4 hours under C, the load capacity of Ga oxides is the 0.5% of catalyst weight in catalyst, obtains corresponding
Supported vanadium-based catalyst.Before prepared catalyst dehydrogenation reaction, by catalyst in CO2550 in atmosphere oUnder C
Processing 2 hours, obtains catalyst O.
【Comparative example 4】
By Yinghuan Fu etc. in Journal of Molecular Catalysis A:Chemical 221(2004)
" the Characterization and reactivity of SnO delivered on 163-1682-doped V2O5/γ-Al2O3
The preparation method system mentioned in catalysts in dehydrogenation of isobutane to isobutene " articles
It is standby to obtain 3wt%SnO2 -10wt%V2O5/Al2O3, it is calculated as catalyst P.
【Embodiment 13】
Catalytic reaction condition
Weigh 0.5g catalyst A and carry out dehydrogenation of isobutane evaluation.Different temperature, pressure, under the conditions of carry out activity comment
Valency, test result is listed in table 1, the data of reaction 6 hours.
The * of table 1
* the iso-butane conversion ratio and selective isobutene of 6 hours is reacted
【Embodiment 14】
Weigh 0.5g catalyst A~P and carry out dehydrogenation of isobutane evaluation.Feeding gas are iso-butane:CO2=1:4；Temperature 560oC；Normal pressure；The mass space velocity (WHSV) of iso-butane is 6.0h-1Under the conditions of carry out activity rating, test result is listed in table 2.
Table 2
| Catalyst | Iso-butane conversion ratio % | Selective isobutene % |
| A | 39.6 | 89.7 |
| B | 39.5 | 89.7 |
| C | 35.2 | 82.4 |
| D | 50.1 | 79.6 |
| E | 35.4 | 83.1 |
| F | 44.3 | 84.9 |
| G | 40.1 | 88.0 |
| H | 38.9 | 88.8 |
| I | 39.5 | 89.4 |
| J | 42.2 | 85.7 |
| K | 38.5 | 90.2 |
| L | 39.9 | 88.8 |
| Comparative example M | 19.3 | 72.5 |
| Comparative example N | 31.7 | 80.1 |
| Comparative example O | 29.6 | 82.8 |
| Comparative example P | 34.2 | 82.2 |
* the iso-butane conversion ratio and selective isobutene of 6 hours is reacted
【Comparative example 5】
Catalyst regenerating stability is contrasted
0.5g catalyst A, 0.5g catalyst M is weighed respectively carries out dehydrogenation of isobutane evaluation.Feeding gas are iso-butane:CO2
=1:4；Temperature 560 oC；Normal pressure；Alkane mass space velocity (WHSV) is 6.0h-1Under the conditions of carry out catalytic dehydrogenation activity rating, enter
Material is after 40 hours, 560 oC is in CO2Regenerated 5 hours under atmosphere, the catalyst reaction performance row after circular response/regeneration 10 times
In table 3.
The * of table 3
* the iso-butane conversion ratio and selective isobutene of 6 hours is reacted.
Claims (11)
1. a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, by weight percentage comprising following components：
A) using silica-base material as carrier, carrier is the 79~98.8% of catalyst weight；
B) using V oxides as active component, active component is the 1~10% of catalyst weight；
C) using the oxide of rare earth element as auxiliary agent, the rare earth oxide is the 0.1~10% of catalyst weight；
D) using the oxide of Group IIIA element as auxiliary agent, the Group IIIA element oxide for catalyst weight 0.1~
1.0%；
The synthesis preparation method that the catalyst activity component barium oxide loads to carrier is comprised the steps of：
1)V2O5The alkoxide compound V (OR) for obtaining vanadium is reacted with fatty alcohol ROH3O, wherein, R is methyl, ethyl, propyl group, fourth
Base, the tert-butyl group or isopropyl, reaction temperature are 60 DEG C~120 DEG C, and the reaction time is 10~48 hours；
2) by the alkoxide compound V (OR) of vanadium3O is dissolved at least one organic solvent in toluene, benzene, acetone or ether, so
After be impregnated on silicon substrate carrier, wherein dipping temperature be 10 DEG C~60 DEG C, dip time be 1~24 hour, the alkoxylate of vanadium
Compound V (OR)3O is completed after reaction with silicon substrate carrier surface hydroxyl, through drying and being calcined, and drying temperature is 90 DEG C~150 DEG C, is done
The dry time is 1~24 hour, and sintering temperature is 400 DEG C~650 DEG C, and roasting time is 1~24 hour, produces corresponding support type
Catalytic component based on vanadium.
2. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that the low-carbon alkanes
For propane or iso-butane.
3. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that the silica-base material
The one kind of carrier in SBA-15, MCM-41 or MCM-48.
4. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that active component is to urge
The 2~8% of agent weight.
5. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that the rare-earth oxidation
At least one of the thing auxiliary agent in La and Ce, rare earth oxide auxiliary agent is the 0.5~5% of catalyst weight.
6. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that the Group IIIA member
At least one of the plain auxiliary agent in Ga and In, the oxide of Group IIIA element is the 0.1~0.8% of catalyst weight.
7. it is used for the catalyst of manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, it is characterised in that catalyst is in catalysis
Preprocessing process can be carried out before reaction, preprocessing process is in CO by catalyst2In atmosphere 1~10 is handled at 400 DEG C~600 DEG C
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 described to urge
The synthesis preparation method that agent active component barium oxide loads to carrier is comprised the steps of：
1)V2O5The alkoxide compound V (OR) for obtaining vanadium is reacted with fatty alcohol ROH3O, wherein, R is methyl, ethyl, propyl group, fourth
Base, the tert-butyl group or isopropyl, reaction temperature are 60 DEG C~120 DEG C, and the reaction time is 10~48 hours；
2) by the alkoxide compound V (OR) of vanadium3O is dissolved at least one organic solvent in toluene, benzene, acetone or ether, so
After be impregnated on silicon substrate carrier, wherein dipping temperature be 10 DEG C~60 DEG C, dip time be 1~24 hour, the alkoxylate of vanadium
Compound V (OR)3O is completed after reaction with silicon substrate carrier surface hydroxyl, through drying and being calcined, and drying temperature is 90 DEG C~150 DEG C, is done
The dry time is 1~24 hour, and sintering temperature is 400 DEG C~650 DEG C, and roasting time is 1~24 hour, produces corresponding support type
Catalytic component based on vanadium；
The synthesis preparation method that the catalyst promoter component rare earth element and Group IIIA element oxide load to carrier is included
Following steps：
1) the medium volume impregnation of soluble salt solution for silicon substrate carrier being firstly added into rare earth element, dipping temperature is 10 DEG C~80
DEG C, dip time is 1~24 hour；
2) by step 1) dipping after silicon substrate carrier be dried, be calcined, drying temperature be 90 DEG C~150 DEG C, drying time is 1
~24 hours, sintering temperature was 400 DEG C DEG C~650 DEG C, and roasting time is 1~24 hour；
3) by step 2) silicon substrate carrier after dipping is then added to the medium volume impregnation of soluble salt solution of Group IIIA element, dipping
Temperature is 10 DEG C~80 DEG C, and dip time is 1~24 hour；
4) by step 3) dipping after silicon substrate carrier be dried, be calcined, produce corresponding loaded catalyst, wherein dry temperature
Spend for 90 DEG C~150 DEG C, drying time is 1~24 hour, sintering temperature is 400 DEG C~650 DEG C, roasting time is 1~24 small
When.
9. preparation method according to claim 8, it is characterised in that the catalyst promoter component rare earth element and IIIA
The synthesis preparation method that race's element oxide loads to carrier is comprised the steps of：
1) silicon substrate carrier is added to the medium volume impregnation of mixed solution of the soluble salt of rare earth element and Group IIIA element, dipping temperature
Spend for 10 DEG C~80 DEG C, dip time is 1~24 hour；
2) by step 1) dipping after silicon substrate carrier be dried, be calcined, produce corresponding loaded catalyst, wherein dry temperature
Spend for 90 DEG C~150 DEG C, drying time is 1~24 hour, sintering temperature is 400 DEG C~650 DEG C, roasting time is 1~24 small
When.
10. a kind of method of manufacturing olefin by low-carbon alkane dehydrogenation, with iso-butane and CO2For raw material, iso-butane and CO2Volume ratio is 1：1
~1：10, reaction temperature is 400 DEG C~600 DEG C, and reaction pressure is 0.08MPa~0.15MPa, and the mass space velocity of iso-butane is
4.0~10.0h-1, raw material after any one of the claim 1~7 catalyst haptoreaction with obtaining low-carbon alkene.
11. the method for manufacturing olefin by low-carbon alkane dehydrogenation according to claim 10, it is characterised in that iso-butane and CO2Volume ratio
For 1：1~1：5.
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| CN106582800A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of isobutane for preparing isobutene |
| CN106582775B (en) * | 2015-10-16 | 2020-08-07 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene |
| CN115430455B (en) * | 2021-06-03 | 2024-06-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dehydrogenating V-base propane and preparation method thereof |
| CN115400748B (en) * | 2022-09-20 | 2023-09-08 | 中国科学院山西煤炭化学研究所 | Isobutane CO 2 Vanadium-based catalyst for oxidative dehydrogenation to prepare isobutene and preparation thereof |
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