CN107486195B - Preparation method of low-carbon alkane dehydrogenation catalyst - Google Patents

Preparation method of low-carbon alkane dehydrogenation catalyst Download PDF

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CN107486195B
CN107486195B CN201610412871.3A CN201610412871A CN107486195B CN 107486195 B CN107486195 B CN 107486195B CN 201610412871 A CN201610412871 A CN 201610412871A CN 107486195 B CN107486195 B CN 107486195B
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catalyst
low
dehydrogenation catalyst
alkane dehydrogenation
drying
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CN107486195A (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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    • 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
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    • 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
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    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/864—Cobalt and chromium
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    • 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
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • 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
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    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • 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

Abstract

The invention discloses a preparation method of a low-carbon alkane dehydrogenation catalyst, which comprises the steps of dissolving a high-valence chromium precursor in a reducing agent solution, dipping the high-valence chromium precursor into an alumina-based carrier, reacting at the reaction temperature of 30-200 ℃ for 0.5-20 h, washing, filtering, drying, dipping an auxiliary agent, drying and roasting to obtain the low-carbon alkane dehydrogenation catalyst. The method has the advantages that the Cr clusters are controllable, the catalyst with moderate Cr dispersion degree is obtained by an in-situ reduction method, the acid content of B on the surface of the catalyst is reduced, the utilization efficiency of active atom Cr is improved, and the dehydrogenation activity, selectivity and anti-carbon deposition performance of the catalyst are improved.

Description

Preparation method of low-carbon alkane dehydrogenation catalyst
Technical Field
The invention relates to a preparation method of a low-carbon alkane dehydrogenation catalyst, in particular to a preparation method of a catalyst for preparing propylene by propane dehydrogenation and preparing butylene by butane dehydrogenation.
Background
In recent years, with the rapid development of the global petrochemical industry, the demand for low-carbon olefins is increasing. The low-carbon alkane dehydrogenation technology is an effective way for increasing the yield of C3-C4 olefins.
The catalytic dehydrogenation reaction of the low-carbon alkane is limited by thermodynamic equilibrium and needs to be carried out under the harsh conditions of high temperature and low pressure. The excessive temperature causes the alkane cracking reaction and deep dehydrogenation to be intensified and the selectivity to be reduced; meanwhile, the carbon deposition on the surface of the catalyst is accelerated, so that the catalyst is quickly deactivated.
At present, foreign enterprises have developed a plurality of sets of industrial technologies for preparing butylene by butane catalytic dehydrogenation, and the matched dehydrogenation catalysts are Pt/Al respectively2O3Catalyst system and chromium oxide/alumina (Cr)2O3/Al2O3) Is a catalyst.
A conventional chromia/alumina catalyst is generally prepared by an impregnation method, and CN86104031A discloses a method for preparing a C3-C5 paraffin dehydrogenation catalyst, which comprises roasting alumina having a microspherical shape twice, impregnating the roasted product with a solution containing chromium and potassium compounds, drying, impregnating the obtained product with a solution containing silicon compounds, and finally drying and roasting. The isobutane dehydrogenation conversion was 53% and the selectivity was 88%, the propane dehydrogenation conversion was 46% and the selectivity was 82%. CN1213662A prepares a microspherical catalyst for a fluidized bed, wherein the chromium content of the catalytic system is 6-30 percent, and K is20.4-3% of O, 0.08-3% of silicon oxide, 0.1-3.5% of tin, and aluminum oxide for complementing to 100%.
CN1185994A discloses a catalyst for preparing isobutene by catalytic dehydrogenation of isobutane, which is represented by a catalyst prepared by a coprecipitation method and a slurry mixing methodFormula is AaBbCcDdOxThe supported catalyst prepared by the impregnation method has the formula: a. theaBbCcThe carrier is Cr, the element B is Cu and La, the element C is K, the element D is Al, and the carrier for loading the catalyst is gamma-Al2O3. At the space velocity of isobutane of 400h-1When the method is used, the isobutane conversion rate is not more than 60 percent, and the selectivity is about 93 percent.
US2010/0312035 discloses a dehydrogenation catalyst consisting of chromium oxide, lithium oxide, sodium oxide, aluminum oxide and alkaline earth metal oxides. CN104010725A silica-stabilized alumina powders prepared by spray drying bayerite powder, precipitating silica with an acid in a bayerite slurry, or impregnating bayerite with or co-extruding with a sodium silicate solution were found to be better catalyst support precursors and catalysts prepared with these silica containing support materials have a higher hydrothermal stability.
CN103447065A relates to a butane dehydrogenation catalyst and a preparation method thereof, the butane dehydrogenation catalyst comprises, by weight, 12-20 parts of chromium oxide, 1-2 parts of potassium oxide, 1-2 parts of vanadium pentoxide, 1-2 parts of silicon dioxide, and the balance of a molecular sieve to 100. the process comprises the steps of ⑴ impregnation, impregnation of the molecular sieve with a solution containing chromium, potassium and vanadium compounds, drying of the product, ⑵ lattice fixation, fixation of active component lattices of the product dried in step ⑴ with a solution of silicon compounds, ⑶ product calcination, heating and calcination of the product dried in step ⑵ at a certain heating speed until 600 ℃ is reached, and heat preservation for 1 hour.
CN101940922 discloses a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein the catalyst uses chromium-containing alumina as a carrier, wherein the weight content of chromium oxide in the carrier is 2.0-15%, and the method for introducing chromium as an active metal component into the alumina carrier is to partially use a kneading method, partially use an impregnation method, and use a three-step roasting method and a hydrothermal method to treat pseudo-boehmite mixed with chromium, so that the pore structure and the surface property of the carrier can be improved, the content and the distribution of the active metal chromium in the carrier and the interaction between the metal activity and the alumina can be further adjusted, the activity and the stability of the catalyst are improved, the carbon deposition resistance of the catalyst is enhanced, and the service life of the catalyst is prolonged.
CN103769078A discloses a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein the catalyst uses Al2O3The catalyst is used as a carrier, chromium is used as an active component, alkali metal is used as a cocatalyst component, the weight of the final catalyst is taken as the reference, the content of chromium oxide is 10-30%, the content of alkali metal oxide is 0.5-3.0%, and the balance is alumina, wherein the active component chromium is impregnated on an alumina carrier step by step before and after the alkali metal cocatalyst component is impregnated. The catalyst for preparing olefin by dehydrogenating low-carbon alkane has high activity stability and propylene selectivity when applied to preparing propylene by dehydrogenating propane, and the preparation method is simple and suitable for industrial application.
CN103769079A discloses a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein the catalyst takes La alumina as a carrier, chromium as an active component, and the weight content of an oxide is calculated, the lanthanum oxide content in the final catalyst is 0.1-5.0, the chromium oxide content is 5-20, and La in the La-containing alumina carrier is introduced during gelling in the preparation process of the alumina. The preparation method of the low-carbon alkane dehydrogenation catalyst comprises the following steps: preparing an alumina carrier containing La and loading active component chromium on the alumina containing La by adopting an impregnation method. The dehydrogenation catalyst is applied to the preparation of propylene by propane dehydrogenation, does not contain alkaline oxides, avoids strong interaction between the alkaline oxides and active components, and improves the activity, stability and selectivity of the dehydrogenation catalyst.
The preparation method of the catalyst adopts an impregnation method, the dispersion state of the active component chromium is difficult to regulate and control, and the stability of the catalyst is poor due to excessively high dispersion degree; too low a degree of dispersion can lead to poor activity of the catalyst.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a low-carbon alkane dehydrogenation catalyst, which adjusts the dispersion state of Cr species on a carrier through in-situ reaction, so that the activity, selectivity and stability of the catalyst are correspondingly improved.
The invention provides a preparation method of a low-carbon alkane dehydrogenation catalyst, wherein a high-valence chromium precursor is dissolved in a reducing agent solution, is soaked in an alumina-based carrier, reacts at the reaction temperature of 30-200 ℃ for 0.5-20 h, is washed, filtered and dried, is soaked with an auxiliary agent, and is dried and roasted to obtain the low-carbon alkane dehydrogenation catalyst.
The preparation method of the low-carbon alkane dehydrogenation catalyst is characterized in that the high-valence chromium precursor is preferably CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4One or more of them.
In the preparation method of the low-carbon alkane dehydrogenation catalyst, the reducing agent solution is preferably an aqueous solution of ethylene glycol, glycerol, glucose, oxalic acid or ascorbic acid components.
When the reducing agent solution is an aqueous solution of glucose, oxalic acid or ascorbic acid, the mass concentration of the glucose, oxalic acid or ascorbic acid component is preferably 1 wt% to 60 wt%, and more preferably 3 wt% to 30 wt%.
The preparation method of the low-carbon alkane dehydrogenation catalyst is characterized in that the alumina-based carrier is preferably an alumina carrier or an alumina carrier containing a refractory inorganic oxide; the refractory inorganic oxide is preferably one or more of silicon oxide, zirconium oxide and titanium oxide; the refractory inorganic oxide is preferably present in the alumina-based support in an amount of 5 wt.% or less.
The preparation method of the low-carbon alkane dehydrogenation catalyst, disclosed by the invention, has the advantages that the mol ratio of the reducing agent to the high-valence chromium precursor is preferably 0.1-10: 1, more preferably 0.5 to 5: 1.
The preparation method of the low-carbon alkane dehydrogenation catalyst is characterized in that the auxiliary agent is preferably one or more of nitrate or acetate of Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe and Zn.
The preparation method of the low-carbon alkane dehydrogenation catalyst comprises the following steps of drying and roasting in an air atmosphere, wherein the drying is preferably carried out at the temperature of 60-150 ℃ for 1-8 hours; the roasting is preferably carried out for 1-20 h at 600-750 ℃.
The preparation method of the low-carbon alkane dehydrogenation catalyst provided by the invention has the advantages that the reaction temperature is preferably 60-140 ℃, and the reaction time is preferably 0.5-3 h.
The method has the advantages that the Cr clusters are controllable, the catalyst with moderate Cr dispersion degree is obtained by an in-situ reduction method, the acid content of B on the surface of the catalyst is reduced, the utilization efficiency of active atom Cr is improved, and the dehydrogenation activity, selectivity and anti-carbon deposition performance of the catalyst are improved.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The invention is realized by the following technical scheme: dissolving a precursor of high-valence chromium in a reducing agent solution, soaking the precursor into an alumina-based carrier, reacting for 0.5-20 hours, preferably 0.5-3 hours, at the temperature of 30-200 ℃, preferably 60-140 ℃, then washing, filtering, drying, soaking a functional auxiliary agent, and drying and roasting to obtain the catalyst. Cr in catalyst2O3The content of (A) is 3-20 wt.%, and the content of the auxiliary agent is 0.5-6 wt.%.
The precursor of the high-valence chromium is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4、K2CrO4One or more of (a).
The reducing agent solution is a reagent capable of reducing high-valence chromium into positive-trivalent chromium, and is selected from ethylene glycol, glycerol, or an aqueous solution containing glucose, oxalic acid and ascorbic acid. The reducing agent solution is preferably an aqueous solution of ethylene glycol and glucose. In the present invention, the mass concentration of the aqueous solution containing glucose, oxalic acid, and ascorbic acid is not particularly limited, and the concentration is only required to be able to dissolve the precursor of high valence chromium, and the mass concentration is generally 1 wt.% to 60 wt.%, and preferably 3 wt.% to 30 wt.%.
The alumina-based carrier is an alumina carrier or alumina containing a small amount of other refractory inorganic oxides as a carrier, the other refractory inorganic oxides are one or more of silicon oxide, zirconium oxide and titanium oxide, and the content of the other refractory inorganic oxides in the alumina-based carrier is less than 5 wt.%.
The molar ratio of the reducing agent to the high-valence chromium is 0.1-10: 1, preferably 0.5-5: 1.
The auxiliary agent is one or more of nitrate and acetate of Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe and Zn, and preferably nitrate or acetate of K and Cu.
The catalyst is dried and roasted in an air atmosphere, and the drying is carried out for 1-8 hours at the temperature of 60-150 ℃; the roasting is carried out for 1-20 h at 600-750 ℃.
The catalyst prepared by the method has the following properties: the specific surface area is 80-200 m2·g-1Pore volume of 0.2-0.6 cm3·g-1The average pore diameter is 4-15 nm.
The catalyst is used for catalytic dehydrogenation of alkane components of C3-C6.
Reaction of high-valence chromium with reducing agent to generate Cr2O3By controlling the limiting function of the pore and the reaction condition, Cr2O3The directly generated sub-nanometer clusters are attached to the hole wall, and the cluster size is uniform and can be regulated and controlled in the process. Compared with the methods such as an immersion method, a precipitation method and the like, the method of the in-situ reaction can obtain Cr with different dispersity2O3A base catalyst. The surface of the highly dispersed Cr contains more Cr-OH corresponding to more B acid centers, so that in the dehydrogenation reaction of low-carbon alkane, the deep cracking reaction is easy to induce the rapid carbon deposition of the catalyst to inactivate, the selectivity of the catalyst is poor, and the inactivation speed is high; at low dispersion, the Cr atoms agglomerate into large particles of Cr2O3Because the dehydrogenation reaction of the low-carbon alkane is a surface catalytic reaction, Cr atoms in the particles are completely wrapped, so that the atom utilization efficiency is low, and meanwhile, the Cr atoms in the large particles are low2O3Easy to induce cracking and other side reactions, and relatively low catalytic activity and selectivity. According to the invention, the dispersion state of Cr species on the carrier is effectively regulated and controlled, and the activity, selectivity and stability of the catalyst are correspondingly improved.
Example 1
2.23g(NH4)2Cr2O7Dissolving in 8ml of ethylene glycol, and soaking in 10g of porous gamma-Al in equal volume2O3In the powder. The powder was placed in an oven at 120 ℃ for 4h, washed with deionized water, filtered and dried at 80 ℃ for 2 h. 0.37gKNO3Dissolving in 8ml deionized water, soaking in the treated powder in the same volume, drying at 80 deg.C for 4 hr, calcining at 680 deg.C for 5 hr, molding and sieving to obtain catalyst A.
Comparative example 1
7.08gCr(NO3)3·9H2O、0.37gKNO3Dissolving in 4ml deionized water, soaking in 10g porous gamma-Al in equal volume2O3Drying the powder at 80 ℃ for 4h, roasting at 680 ℃ for 5h, and molding and screening to obtain a catalyst, which is recorded as catalyst B.
Example 2
1.77gCrO3、2.48g(NH4)2C2O4Dissolving in 8ml deionized water, soaking in equal volume to 10g of porousγ-Al2O3In the powder. The powder was placed in an oven at 60 ℃ for 6h, washed with deionized water, filtered and dried at 100 ℃ for 2 h. 0.78gCu (NO)3)2·3H2O、1.12gFe(NO3)3·9H2Dissolving O in 7ml deionized water, soaking in the treated powder in the same volume, drying at 120 deg.C for 3 hr, calcining at 700 deg.C for 6 hr, molding and sieving to obtain catalyst C.
Comparative example 2
7.08gCr(NO3)3·9H2O、0.78gCu(NO3)2·3H2O、1.12gFe(NO3)3·9H2Dissolving O in 3.5ml deionized water, soaking in 10g of porous gamma-Al in equal volume2O3Drying the powder at 80 ℃ for 4h, roasting the powder at 700 ℃ for 6h, and forming and screening the powder to obtain a catalyst which is recorded as a catalyst D.
Example 3
1.30gK2Cr2O7Dissolving in 8ml of glycerol, and soaking in 10g of porous gamma-Al in equal volume2O3In the powder. The powder was placed in an oven at 140 ℃ for 1h, washed with deionized water, filtered and dried at 80 ℃ for 4 h. 0.33g NaNO3、0.82gNi(NO3)2·6H2Dissolving O in 8ml deionized water, soaking in the treated powder in the same volume, drying at 60 deg.C for 6 hr, calcining at 720 deg.C for 4 hr, molding and sieving to obtain catalyst, which is designated as catalyst E.
Comparative example 3
3.54gCr(NO3)3·9H2O、0.33gNaNO3、0.82gNi(NO3)2·6H2Dissolving O in 6.0ml deionized water, soaking in 10g porous gamma-Al in equal volume2O3Drying the powder at 80 deg.C for 4 hr, calcining at 720 deg.C for 4 hr, and sieving to obtain catalyst F.
Example 4
2.30gNa2CrO40.39g of glucose was dissolved in 8ml of deionized water and the solution was immersed in 10g of porous gamma-Al in the same volume2O3In the powder. The powder is placed in an oven at 85 ℃ for treatment for 4h and is usedWashing with ionized water, filtering, and drying at 95 deg.C for 3 hr. 0.37gKNO3、0.32gLa(NO3)3·6H2O、1.14gFe(NO3)2·9H2Dissolving O in 7ml deionized water, soaking in the treated powder in the same volume, drying at 70 deg.C for 5 hr, calcining at 690 deg.C for 6 hr, molding and sieving to obtain catalyst G.
Comparative example 4
5.66gCr(NO3)3·9H2O、0.37gKNO3、0.32gLa(NO3)3·6H2O、1.14gFe(NO3)2·9H2Dissolving O in 4.8ml deionized water, soaking in 10g of porous gamma-Al in equal volume2O3Drying the powder at 80 ℃ for 4H, roasting the powder at 690 ℃ for 6H, and forming and screening the dried powder to obtain a catalyst which is recorded as a catalyst H.
Example 5
3.77gK2CrO42.82g ascorbic acid in 8ml deionized water, and soaking in 10g porous gamma-Al in equal volume2O3In the powder. The powder was placed in an oven at 60 ℃ for 1h, washed with deionized water, filtered and dried at 80 ℃ for 4 h. 0.28gKNO3、0.65gCu(NO3)2·3H2Dissolving O in 8ml deionized water, soaking in the treated powder in the same volume, drying at 60 deg.C for 6 hr, calcining at 720 deg.C for 4 hr, molding and sieving to obtain catalyst I.
Comparative example 5
7.79gCr(NO3)3·9H2O、0.28gKNO3、0.65gCu(NO3)2·3H2Dissolving O in 3.0ml deionized water, soaking in 10g porous gamma-Al in equal volume2O3Drying the powder at 80 deg.C for 4 hr, calcining at 720 deg.C for 4 hr, and sieving to obtain catalyst J.
Example 6
3.23g(NH4)2CrO4Dissolving in 8ml of ethylene glycol, and soaking in 10g of porous gamma-Al in equal volume2O3In the powder. The powder is placed in an oven at 150 deg.C for 0.5h, washed with deionized water, filtered, and heated at 80 deg.CDrying for 2 h. 0.28gKNO3、0.65gCu(NO3)2·3H2Dissolving O in 8ml deionized water, soaking the powder in the same volume, drying at 80 deg.C for 4 hr, calcining at 680 deg.C for 8 hr, and sieving to obtain catalyst K.
Comparative example 6
3.23g(NH4)2CrO4、0.28gKNO3、0.65gCu(NO3)2·3H2Dissolving O in 7.6ml deionized water, soaking in the treated powder in the same volume, drying at 80 deg.C for 4 hr, calcining at 680 deg.C for 8 hr, molding and sieving to obtain catalyst L.
The catalysts prepared in the above examples are evaluated on a micro-reactor, and the evaluation conditions of the catalytic dehydrogenation of propane are as follows: volume space velocity of 1200h-1The reaction temperature is 610 ℃, and the reaction pressure is normal pressure; the evaluation conditions of catalytic dehydrogenation of isobutane are as follows: volume space velocity of 600h-1The reaction temperature is 590 ℃, and the reaction pressure is normal pressure.
Example 7
1.66g(NH4)2Cr2O7、1.63gNa2CrO40.92g of glucose was dissolved in 8ml of deionized water and the solution was immersed in 10g of porous gamma-Al in the same volume2O3In the powder. The powder was placed in an oven at 95 ℃ for 2h, washed with deionized water, filtered and dried at 60 ℃ for 10 h. 0.16gCa (NO)3)2·4H2O、0.11gSr(NO3)2、2.33gCo(NO3)2·6H2Dissolving O in 7ml deionized water, soaking in the treated powder in the same volume, drying at 80 deg.C for 4 hr, calcining at 750 deg.C for 10 hr, molding and sieving to obtain catalyst M.
Comparative example 7
9.3gCr(NO3)3·9H2O、0.16gCa(NO3)2·4H2O、0.11gSr(NO3)2、2.33gCo(NO3)2·6H2Dissolving O in 3.8ml deionized water, soaking in 10g of porous gamma-Al in equal volume2O3Drying the powder at 80 deg.C for 4 hr, and at 750 deg.CRoasting for 10h, and obtaining the catalyst which is recorded as catalyst N after molding and screening.
TABLE 1 evaluation of the Activity of the catalyst
Figure BDA0001015260870000081
As can be seen from the catalyst evaluation results of table 1, the catalyst (A, C, E, G, I, K, M) synthesized using in situ reduction was superior in conversion, selectivity, and stability to the corresponding directly impregnated catalyst (B, D, F, H, J, L, N). The catalyst performance is further improved by changing the reaction conditions in the preparation process and optimizing the auxiliary agent. The initial yield of propane dehydrogenation is more than 46 percent, and the initial yield of isobutane dehydrogenation is more than 62.2 percent.

Claims (9)

1. A preparation method of a low-carbon alkane dehydrogenation catalyst is characterized by dissolving a high-valence chromium precursor in a reducing agent solution, soaking the high-valence chromium precursor in an alumina-based carrier, reacting at the reaction temperature of 30-200 ℃ for 0.5-20 h, then washing, filtering, drying, soaking an auxiliary agent, drying and roasting to obtain the low-carbon alkane dehydrogenation catalyst;
wherein the reducing agent solution is an aqueous solution of ethylene glycol, glycerol, glucose, oxalic acid or ascorbic acid components;
the molar ratio of the reducing agent to the high-valence chromium precursor is 0.1-10: 1.
2. the method of claim 1, wherein the high valence cr precursor is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4One or more of them.
3. The method for preparing the low carbon alkane dehydrogenation catalyst according to claim 1, wherein when the reducing agent solution is an aqueous solution of a glucose, oxalic acid or ascorbic acid component, the mass concentration of the glucose, oxalic acid or ascorbic acid component is 1 wt.% to 60 wt.%.
4. The method for preparing the low carbon alkane dehydrogenation catalyst according to claim 3, wherein when the reducing agent solution is an aqueous solution of a glucose, oxalic acid or ascorbic acid component, the mass concentration of the glucose, oxalic acid or ascorbic acid component is 3 wt.% to 30 wt.%.
5. The method for preparing a light alkane dehydrogenation catalyst according to claim 1, wherein the alumina-based support is an alumina support or an alumina support containing a refractory inorganic oxide; the refractory inorganic oxide is one or more of silicon oxide, zirconium oxide and titanium oxide; the refractory inorganic oxide is present in the alumina-based support in an amount of 5 wt.% or less.
6. The method for preparing the light alkane dehydrogenation catalyst according to claim 1, wherein the molar ratio of the reducing agent to the high-valence chromium precursor is 0.5-5: 1.
7. The method for preparing the low-carbon alkane dehydrogenation catalyst according to any one of claims 1 to 5, wherein the auxiliary agent is one or more of nitrate or acetate of Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe and Zn.
8. The method for preparing the low-carbon alkane dehydrogenation catalyst according to any one of claims 1 to 5, wherein the drying and roasting are carried out in an air atmosphere, and the drying is carried out at 60 to 150 ℃ for 1 to 8 hours; the roasting is carried out for 1-20 h at 600-750 ℃.
9. The method for preparing the light alkane dehydrogenation catalyst according to any one of claims 1 to 5, wherein the reaction temperature is 60 to 140 ℃ and the reaction time is 0.5 to 3 hours.
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