CN107486195A - The preparation method of catalyst for dehydrogenation of low-carbon paraffin - Google Patents

The preparation method of catalyst for dehydrogenation of low-carbon paraffin Download PDF

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CN107486195A
CN107486195A CN201610412871.3A CN201610412871A CN107486195A CN 107486195 A CN107486195 A CN 107486195A CN 201610412871 A CN201610412871 A CN 201610412871A CN 107486195 A CN107486195 A CN 107486195A
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catalyst
dehydrogenation
low
preparation
carbon paraffin
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CN107486195B (en
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周金波
邹国军
李长明
王艳飞
苟文甲
程中克
郭珺
李博
唐迎春
马艳捷
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Petrochina Co Ltd
Lanzhou Institute of Chemical Physics LICP of CAS
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Petrochina Co Ltd
Lanzhou Institute of Chemical Physics LICP of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/862—Iron and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/864—Cobalt and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/866—Nickel and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/86—Chromium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, high valence chrome predecessor is dissolved in reductant solution, it is impregnated into alumina-based supports, it it is 30~200 DEG C in reaction temperature, reaction time reacts under conditions of being 0.5~20h, it is washed out, filters, after drying, impregnation aids, then obtain catalyst for dehydrogenation of low-carbon paraffin after drying, roasting.It is an advantage of the invention that Cr clusters are controllable, the catalyst of moderate Cr decentralization is obtained by the method for in-situ reducing, reduces catalyst surface B acid acid amounts, improves active atomic Cr utilization ratio, the dehydrogenation activity of catalyst, selectivity, anti-carbon performance improve.

Description

The preparation method of catalyst for dehydrogenation of low-carbon paraffin
Technical field
The present invention relates to a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, particularly a kind of preparing propylene by dehydrogenating propane and The preparation method of the catalyst of butane dehydrogenation butylene.
Background technology
In recent years, it is also growing to the demand of low-carbon alkene with the fast development of Global Oil chemical industry.Low-carbon Dehydrating alkanes technology is to increase production the effective way of C3~C4 alkene.
Low-carbon alkanes catalytic dehydrogenating reaction is limited by thermodynamical equilibrium, must high temperature, low pressure harsh conditions under carry out. Too high temperature, decline alkane cracking reaction and deep dehydrogenation aggravation, selectivity；Accelerate catalyst surface carbon distribution simultaneously, make Rapid catalyst deactivation.
At present, overseas enterprise has developed more set catalytic dehydrogenation of butanes butylene industrialization technologies, and supporting dehydrogenation is urged Agent is Pt/Al respectively2O3Series catalysts and chromium oxide/aluminum oxide (Cr2O3/Al2O3) series catalysts.
Traditional chromium oxide/aluminum oxide catalyst is typically prepared using infusion process, and CN86104031A discloses one kind and prepared Aluminum oxide with microballoon shape is carried out double roasting, will be calcined by the method for C3~C5 paraffin hydrocarbon dehydrogenation catalysts, this method Product afterwards is impregnated and dried with the solution containing chromium and potassium compound, then soaks products obtained therefrom with siliceous compound solution Stain, finally it is dried and is calcined.Dehydrogenation of isobutane conversion ratio is 53%, and selectivity is 88%, and dehydrogenating propane conversion ratio is 46%, selectivity is 82%.CN1213662A is prepared for a kind of microspherical catalyst of fluid bed, the catalyst system and catalyzing chromium content 6% ~30%, K2O content 0.4%~3%, silica content 0.08%~3%, Theil indices are 0.1%~3.5%, use aluminum oxide Supply to 100%.
CN1185994A discloses a kind of catalyst for producing isobutylene by catalytic dehydrogenation of isobutane, with coprecipitation and mixes Catalyst expression prepared by slurry processes is AaBbCcDdOx, the expression of the loaded catalyst prepared with infusion process：AaBbCc/ carry Body, elements A Cr, element B are Cu and La, and Elements C K, element D are Al, and the carrier of supported catalyst is γ-Al2O3.Different Butane air speed 400h-1When, iso-butane conversion ratio is not more than 60%, selectivity 93% or so.
US2010/0312035 discloses a kind of dehydrogenation, catalyst composition is chromium oxide, lithia, sodium oxide molybdena, Aluminum oxide and alkaline earth oxide.CN104010725A by be spray-dried bayerite powder, bayerite slurry in Using acid come precipitated silica or using sodium silicate solution come the dioxy that impregnates bayerite or be coextruded and prepare therewith The stable alumina powder of SiClx is found to be preferable catalyst carrier precursor, with these silica containing carrier materials of bag The catalyst of preparation has higher hydrothermal stability.
CN103447065A is related to a kind of butane dehydrogenation catalyst and preparation method.Butane dehydrogenation catalyst is by following material Form by weight percentage：Chrome green：12~20, potassium oxide：1~2, vanadic anhydride：1~2, silica：1~2, Molecular sieve：Supply to 100.Processing step includes：(1) impregnate, molecular sieve is soaked with the solution containing chromium, potassium and vfanadium compound Stain, product are dried；(2) lattice is fixed, and by step, (1) dried product carries out active component crystalline substance with silicon compound solution again Lattice are fixed；(3) product is calcined, and by step, (2) dried product heats roasting with certain rate of warming, until reach 600 DEG C, And it is incubated 1h；Beneficial effect is：The damage and loss of catalyst active phase in use are prevented, improves catalytic mechanical Intensity and longtime running stability.
CN101940922 discloses a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, and the catalyst is with oxygen containing chromium Change aluminium is carrier, and wherein the weight content of chromium oxide in the carrier is 2.0%~15%, and active metal component chromium introduces aluminum oxide Method in carrier is that part uses kneading method, partly using infusion process, and is mixed into using three one-step baking methods and hydro-thermal method processing The boehmite of chromium, it can so improve the pore structure and surface nature of carrier, a step of going forward side by side becomes active metal chromium in carrier In content, the interaction between distribution and metal active and aluminum oxide, not only increase the activity and stability of catalyst, and And the carbon accumulation resisting ability of catalyst is enhanced, extend the service life of catalyst.
CN103769078A discloses a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, and the catalyst is with Al2O3For Carrier, using chromium as active component, using alkali metal as co-catalysis component, on the basis of the weight by final catalyst, chromium oxide contains Measure as 10%~30%, alkali metal oxide content is 0.5%~3.0%, and surplus is aluminum oxide, and described active component chromium exists Impregnate before alkali metal co-catalysis component and after dipping alkali metal co-catalysis component step impregnation on alumina support.Above-mentioned low-carbon Dehydrating alkanes alkene catalyst is applied in preparing propylene by dehydrogenating propane, has high activity stability and Propylene Selectivity, and And preparation method is simple, suitable for commercial Application.
CN103769079A discloses a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, and the catalyst is aoxidized with La Aluminium is carrier, using chromium as active component, in terms of the weight content of oxide, in final catalyst lanthanum oxide content be 0.1~ 5.0, chromic oxide content is 5~20, and the La in alumina support containing La in aluminum oxide preparation process during plastic by introducing.Institute The preparation method of catalyst for dehydrogenation of low-carbon paraffin is stated, is comprised the following steps：The preparation of the alumina support containing La and the oxidation containing La Aluminium uses infusion process load active component chromium process.Described dehydrogenation is applied in preparing propylene by dehydrogenating propane, the catalysis Agent does not contain basic anhydride, avoids the strong interaction between basic anhydride and active component, improves dehydrogenation Activity, the selectivity of stability and propylene.
Above method for preparing catalyst often takes infusion process, and the dispersity of active component chromium is difficult regulation and control, too high point Divergence can cause the stability of catalyst poor；Too low decentralization can cause the poor activity of catalyst.
The content of the invention
In view of the above-mentioned problems, the invention provides a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, by situ anti- Dispersity of the Cr species on carrier should be adjusted, the activity, selectivity and stability of catalyst is accordingly improved.
The present invention provides a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, wherein, high valence chrome predecessor is dissolved in also In former agent solution, it is impregnated into alumina-based supports, is 30~200 DEG C in reaction temperature, the reaction time is 0.5~20h bar Reacted under part, be washed out, filter, after drying, impregnation aids, then obtain catalyst for dehydrogenation of low-carbon paraffin after drying, roasting.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the high valence chrome predecessor is preferably CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4In one or more.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the reductant solution is preferably second Glycol, glycerine, glucose, the aqueous solution of oxalic acid or vitamin c component.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the reductant solution be glucose, During the aqueous solution of oxalic acid or vitamin c component, the mass concentration of glucose, oxalic acid or vitamin c component is preferably 1wt.% ~60wt.%, more preferably 3wt.%~30wt.%.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the alumina-based supports are preferably Alumina support or the alumina support containing refractory inorganic oxides；The refractory inorganic oxides are preferably silica, oxygen Change the one or more in zirconium and titanium oxide；Content of the refractory inorganic oxides in alumina-based supports be preferably Below 5wt.%.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the reducing agent and high valence chrome forerunner The mol ratio of thing is preferably 0.1~10：1, more preferably 0.5~5:1.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the auxiliary agent be preferably Na, K, Ca, One or more of nitrate or acetate in Sr, La, Sn, Cu, Ni, Co, Fe and Zn.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the drying, roasting are in air gas Carried out under atmosphere, 1~8h is preferably dried in the drying at 60~150 DEG C；The roasting preferably roasts at 600~750 DEG C Burn 1~20h.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the reaction temperature is preferably 60~ 140 DEG C, the reaction time is preferably 0.5~3h.
It is an advantage of the invention that Cr clusters are controllable, the catalyst of moderate Cr decentralization is obtained by the method for in-situ reducing, Catalyst surface B acid acid amounts are reduced, improve active atomic Cr utilization ratio, it is the dehydrogenation activity of catalyst, selective, anti- Carbon distribution performance improves.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation The experimental method of unreceipted actual conditions in example, generally according to normal condition.
The present invention is achieved by the following technical solutions：The predecessor of high valence chrome is dissolved in reductant solution, impregnated Into alumina-based supports, under the conditions of temperature is 30~200 DEG C, preferably 60~140 DEG C, 0.5~20h is reacted, is preferably 0.5~3h, it is washed out, filters, after drying, impregnates function additive, then catalyst is obtained after drying, roasting.In catalyst Cr2O3Content be 3wt.%~20wt.%, auxiliary agent content is 0.5wt.%~6wt.%.
The predecessor of described high valence chrome is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、 Na2CrO4、K2CrO4One or more.
Described reductant solution is that high valence chrome can be made to be reduced to the reagent of positive trivalent chromium, selected from ethylene glycol, glycerine, Or containing glucose, oxalic acid, vitamin c component the aqueous solution.Described reductant solution is preferably ethylene glycol and glucose The aqueous solution.In the present invention to it is described containing glucose, oxalic acid, vitamin c component the aqueous solution mass concentration do not make it is special Limit, as long as its concentration can dissolve the predecessor of high valence chrome, its mass concentration is generally 1wt.%~60wt.%, Preferably 3wt.%~30wt.%.
Described alumina-based supports refer to that alumina support or the aluminum oxide containing other a small amount of refractory inorganic oxides are Carrier, other refractory inorganic oxides are generally the one or more of silica, zirconium oxide, titanium oxide, in alumina-based supports In content in below 5wt.%.
The mol ratio 0.1~10 of the reducing agent and high valence chrome：1, preferably 0.5~5:1.
Described auxiliary agent is Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe, Zn one or more nitrate, acetic acid The nitrate or acetate of salt, preferably K and Cu.
Described catalyst is dry, roasting is to carry out in air atmosphere, and described drying is dried at 60~150 DEG C 1~8h；Described roasting is 1~20h of roasting at 600~750 DEG C.
It is as follows using the catalyst property obtained by the inventive method：80~200m of specific surface area2·g-1, pore volume 0.2~ 0.6cm3·g-1, 4~15nm of average pore diameter.
The catalyst is used for the catalytic dehydrogenation of C3~C6 alkane components.
High valence chrome and reducing agent reaction generation Cr2O3, pass through the confinement effect in duct and the regulation and control of reaction condition, Cr2O3Directly Deliver a child into the cluster of sub- nanometer and then be attached on hole wall, cluster size is homogeneous in the process and can regulate and control.Relative to leaching The methods of stain method, precipitation method, the method for this reaction in-situ can obtain the Cr of different decentralization2O3Base catalyst.High degree of dispersion Cr surfaces contain more Cr-OH, corresponding more B acid sites, in dehydrogenating low-carbon alkane reaction, easily cause depth to be split Solution reaction lures the quick carbon distribution of catalyst into and inactivated that the selectivity of catalyst is poor, and deactivation rate is very fast；In low polydispersity situation Under, Cr atoms are gathered into the Cr of bulky grain2O3, because dehydrogenating low-carbon alkane reaction is surface-catalyzed reactions, the Cr inside particle is former Son, which is completely wrapped, causes atom utilization ratio step-down, meanwhile, the Cr of bulky grain2O3The side reactions such as easy inducing lysis occur, phase It is corresponding that there is relatively low catalytic activity and selectivity.The present invention by effectively regulating and controlling dispersity of the Cr species on carrier, Activity, selectivity and the stability of catalyst are accordingly improved.
Embodiment 1
2.23g(NH4)2Cr2O7It is dissolved in 8ml ethylene glycol, incipient impregnation to 10g porous gammas-Al2O3In powder.The powder End is placed into 120 DEG C of baking ovens and handles 4h, is washed with deionized, filters, 2h is dried at 80 DEG C.0.37gKNO38ml is dissolved in go In ionized water, incipient impregnation is dried 4h, 680 DEG C of roasting 5h, sieved through overmolding into above-mentioned treated powder at 80 DEG C Obtain catalyst and be denoted as catalyst A.
Comparative example 1
7.08gCr(NO3)3·9H2O、0.37gKNO3It is dissolved in 4ml deionized waters, incipient impregnation to 10g porous gammas- Al2O3In powder, 4h, 680 DEG C of roasting 5h are dried at 80 DEG C, sieves to obtain catalyst through overmolding and is denoted as catalyst B.
Embodiment 2
1.77gCrO3、2.48g(NH4)2C2O4It is dissolved in 8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3 In powder.Powder is placed into 60 DEG C of baking ovens and handles 6h, is washed with deionized, filters, 2h is dried at 100 DEG C.0.78gCu (NO3)2·3H2O、1.12gFe(NO3)3·9H2O is dissolved in 7ml deionized waters, incipient impregnation to above-mentioned treated powder In, 3h, 700 DEG C of roasting 6h are dried at 120 DEG C, sieves to obtain catalyst through overmolding and is denoted as catalyst C.
Comparative example 2
7.08gCr(NO3)3·9H2O、0.78gCu(NO3)2·3H2O、1.12gFe(NO3)3·9H2O be dissolved in 3.5ml go from In sub- water, incipient impregnation to 10g porous gammas-Al2O3In powder, 4h is dried at 80 DEG C, 700 DEG C of roasting 6h, is sieved through overmolding Obtain catalyst and be denoted as catalyst D.
Embodiment 3
1.30gK2Cr2O7It is dissolved in 8ml glycerine, incipient impregnation to 10g porous gammas-Al2O3In powder.Powder is placed 1h is handled into 140 DEG C of baking ovens, is washed with deionized, filters, 4h is dried at 80 DEG C.0.33gNaNO3、0.82gNi (NO3)2·6H2O is dissolved in 8ml deionized waters, and incipient impregnation is into above-mentioned treated powder, dry 6h at 60 DEG C, and 720 DEG C roasting 4h, sieves to obtain catalyst and is denoted as catalyst E through overmolding.
Comparative example 3
3.54gCr(NO3)3·9H2O、0.33gNaNO3、0.82gNi(NO3)2·6H2O is dissolved in 6.0ml deionized waters, Incipient impregnation is to 10g porous gammas-Al2O3In powder, 4h is dried at 80 DEG C, 720 DEG C of roasting 4h, sieves and is urged through overmolding Agent is denoted as catalyst F.
Embodiment 4
2.30gNa2CrO4, 0.39g glucose be dissolved in 8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3 In powder.Powder is placed into 85 DEG C of baking ovens and handles 4h, is washed with deionized, filters, 3h is dried at 95 DEG C.0.37gKNO3、 0.32gLa(NO3)3·6H2O、1.14gFe(NO3)2·9H2O is dissolved in 7ml deionized waters, and incipient impregnation treats to above-mentioned Powder in, 5h, 690 DEG C of roasting 6h are dried at 70 DEG C, sieves to obtain catalyst through overmolding and is denoted as catalyst G.
Comparative example 4
5.66gCr(NO3)3·9H2O、0.37gKNO3、0.32gLa(NO3)3·6H2O、1.14gFe(NO3)2·9H2O is molten In 4.8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3In powder, 4h, 690 DEG C of roasting 6h are dried at 80 DEG C, Sieve to obtain catalyst through overmolding and be denoted as catalyst H.
Embodiment 5
3.77gK2CrO4, 2.82g ascorbic acid be dissolved in 8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3 In powder.Powder is placed into 60 DEG C of baking ovens and handles 1h, is washed with deionized, filters, 4h is dried at 80 DEG C.0.28gKNO3、 0.65gCu(NO3)2·3H2O is dissolved in 8ml deionized waters, and incipient impregnation is dried into above-mentioned treated powder at 60 DEG C 6h, 720 DEG C of roasting 4h, sieve to obtain catalyst and are denoted as catalyst I through overmolding.
Comparative example 5
7.79gCr(NO3)3·9H2O、0.28gKNO3、0.65gCu(NO3)2·3H2O is dissolved in 3.0ml deionized waters, etc. Volume impregnation is to 10g porous gammas-Al2O3In powder, 4h is dried at 80 DEG C, 720 DEG C of roasting 4h, sieves and is catalyzed through overmolding Agent is denoted as catalyst J.
Embodiment 6
3.23g(NH4)2CrO4It is dissolved in 8ml ethylene glycol, incipient impregnation to 10g porous gammas-Al2O3In powder.The powder It is placed into 150 DEG C of baking ovens and handles 0.5h, is washed with deionized, filters, 2h is dried at 80 DEG C.0.28gKNO3、0.65gCu (NO3)2·3H2O is dissolved in 8ml deionized waters, and incipient impregnation is into above-mentioned treated powder, dry 4h at 80 DEG C, and 680 DEG C roasting 8h, sieves to obtain catalyst and is denoted as catalyst K through overmolding.
Comparative example 6
3.23g(NH4)2CrO4、0.28gKNO3、0.65gCu(NO3)2·3H2O is dissolved in 7.6ml deionized waters, in equal volume It is impregnated into above-mentioned treated powder, 4h, 680 DEG C of roasting 8h is dried at 80 DEG C, sieves to obtain catalyst through overmolding and be denoted as Catalyst L.
The catalyst prepared by various embodiments above is taken to be evaluated on micro-reactor, propane catalytic dehydrogenation appreciation condition is： Volume space velocity 1200h-1, 610 DEG C of reaction temperature, reaction pressure is normal pressure；Catalytic dehydrogenation of isobutane appreciation condition is：Volume space velocity 600h-1, 590 DEG C of reaction temperature, reaction pressure is normal pressure.
Embodiment 7
1.66g(NH4)2Cr2O7、1.63gNa2CrO4, 0.92g glucose be dissolved in 8ml deionized waters, incipient impregnation arrives 10g porous gammas-Al2O3In powder.The powder is placed into 95 DEG C of baking ovens and handles 2h, is washed with deionized, filters, at 60 DEG C Dry 10h.0.16gCa(NO3)2·4H2O、0.11gSr(NO3)2、2.33gCo(NO3)2·6H2O is dissolved in 7ml deionized waters, Incipient impregnation dries 4h, 750 DEG C of roasting 10h, sieves and be catalyzed through overmolding into above-mentioned treated powder at 80 DEG C Agent is denoted as catalyst M.
Comparative example 7
9.3gCr(NO3)3·9H2O、0.16gCa(NO3)2·4H2O、0.11gSr(NO3)2、2.33gCo(NO3)2·6H2O It is dissolved in 3.8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3In powder, 4h, 750 DEG C of roastings are dried at 80 DEG C 10h, sieves to obtain catalyst and is denoted as catalyst n through overmolding.
The activity rating of the catalyst of table 1
The catalyst (A, C, E, G, I, K, M) synthesized using in-situ reducing is can be seen that from the evaluating catalyst result of table 1 to turn Better than the catalyst (B, D, F, H, J, L, N) of corresponding direct impregnation in rate, selectivity and stability.Prepared by change Reaction condition, optimization auxiliary agent in journey, catalyst performance have further raising.Dehydrogenating propane starting yield ＞ 46%, iso-butane Dehydrogenation starting yield ＞ 62.2%.

Claims (11)

1. a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, it is characterised in that it is molten that high valence chrome predecessor is dissolved in reducing agent In liquid, it is impregnated into alumina-based supports, is 30~200 DEG C in reaction temperature, the reaction time is anti-under conditions of 0.5~20h Should, it is washed out, filters, after drying, impregnation aids, then obtain catalyst for dehydrogenation of low-carbon paraffin after drying, roasting.
2. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, it is characterised in that the high valence chrome forerunner Thing is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4In one or more.
3. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, it is characterised in that the reductant solution For the aqueous solution of ethylene glycol, glycerine, glucose, oxalic acid or vitamin c component.
4. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 3, it is characterised in that the reductant solution For glucose, oxalic acid or vitamin c component the aqueous solution when, the mass concentration of glucose, oxalic acid or vitamin c component is 1wt.%~60wt.%.
5. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 4, it is characterised in that the reductant solution For glucose, oxalic acid or vitamin c component the aqueous solution when, the mass concentration of glucose, oxalic acid or vitamin c component is 3wt.%~30wt.%.
6. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, it is characterised in that the aluminum oxide base load Body is alumina support or the alumina support containing refractory inorganic oxides；The refractory inorganic oxides are silica, oxygen Change the one or more in zirconium and titanium oxide；Content of the refractory inorganic oxides in alumina-based supports be 5wt.% with Under.
7. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin as described in any one of claim 1~6, it is characterised in that described The mol ratio of reducing agent and high valence chrome predecessor is 0.1~10：1.
8. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 7, it is characterised in that the reducing agent and height The mol ratio of valency chromium predecessor is 0.5~5:1.
9. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin as described in any one of claim 1~6, it is characterised in that described Auxiliary agent is one or more of nitrate or acetate in Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe and Zn.
10. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin as described in any one of claim 1~6, it is characterised in that described It is to carry out in air atmosphere to dry, be calcined, and the drying is that 1~8h is dried at 60~150 DEG C；The roasting is 600 1~20h is calcined at~750 DEG C.
11. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin as described in any one of claim 1~6, it is characterised in that described Reaction temperature is 60~140 DEG C, and the reaction time is 0.5~3h.
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