CN107486197B - Preparation method of low-carbon alkane dehydrogenation microspherical catalyst - Google Patents

Preparation method of low-carbon alkane dehydrogenation microspherical catalyst Download PDF

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CN107486197B
CN107486197B CN201610420896.8A CN201610420896A CN107486197B CN 107486197 B CN107486197 B CN 107486197B CN 201610420896 A CN201610420896 A CN 201610420896A CN 107486197 B CN107486197 B CN 107486197B
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catalyst
alumina
low
drying
carbon alkane
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CN107486197A (en
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周金波
王晓来
李博
王栋
李秋颖
程中克
郭珺
董炳利
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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    • 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
    • B01J23/70—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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing

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Abstract

A preparation method of a low-carbon alkane dehydrogenation microspherical catalyst comprises the following steps: dissolving a high-valence chromium precursor in a reducing agent solution, soaking the precursor into an alumina microsphere carrier, reacting at the reaction temperature of 30-200 ℃ for 0.5-20 h, washing, filtering, drying, soaking an auxiliary agent, drying, and roasting to obtain a catalyst; the alumina microsphere carrier comprises macroporous alumina with the weight content of 30-80% and inorganic oxide binder with the weight content of 20-70%. The method has the advantages that the Cr clusters of the microspherical catalyst 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 carbon deposition resistance of the catalyst are improved.

Description

Preparation method of low-carbon alkane dehydrogenation microspherical 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 microspherical 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, wherein the catalyst prepared by a coprecipitation method and a slurry mixing method has a formula 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 microspherical catalyst, which adjusts the dispersion state of Cr species on a carrier through in-situ reaction, and correspondingly improves the activity, selectivity and stability of the catalyst.
The invention provides a preparation method of a low-carbon alkane dehydrogenation microspherical catalyst, which comprises the following steps: dissolving a precursor of high-valence chromium in a reducing agent or a reducing agent solution, then soaking the precursor into an alumina microsphere carrier, reacting at the reaction temperature of 30-200 ℃ for 0.5-20 h, then washing, filtering and drying, soaking an auxiliary agent, and drying and roasting to obtain a catalyst;
the alumina microsphere carrier comprises macroporous alumina with the weight content of 30-80% and inorganic oxide binder with the weight content of 20-70%.
The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst is characterized in that the macroporous alumina preferably has a pseudo-boehmite structure, a monohydrate bauxite structure or a gibbsite structure.
The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst comprises the following steps of (1) preferably, the content of sodium oxide in macroporous alumina is less than or equal to 0.3% and the content of silicon dioxide is less than or equal to 0.3% by mass of macroporous alumina 100%; the pore volume of the macroporous alumina is preferably 0.7-1.4 ml/g.
The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst is characterized in that the inorganic oxide binder is preferably aluminum sol and/or pseudo-boehmite.
The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst comprises the following steps of when the inorganic oxide binder is a mixture of aluminum sol and pseudo-boehmite, wherein the mass ratio of the alumina from the pseudo-boehmite to the alumina from the aluminum sol is preferably 1: 1-5: 1.
the preparation method of the low-carbon alkane dehydrogenation microspherical catalyst is characterized in that the precursor of the high-valence chromium is preferably CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4One or more of them.
The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst is characterized in that the reducing agent is preferably glycol or glycerol; the reducing agent solution is preferably an aqueous solution containing a glucose, oxalic or ascorbic component.
The preparation method of the low-carbon alkane dehydrogenation microsphere catalyst, provided by the invention, comprises the step of, when the reducing agent solution is an aqueous solution of glucose, oxalic acid or ascorbic acid components, preferably, the mass concentration of the glucose, oxalic acid or ascorbic acid components is 1 wt% to 60 wt%, and more preferably, the mass concentration of the glucose, oxalic acid or ascorbic acid components is 3 wt% to 30 wt%.
The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst, disclosed by the invention, is characterized in that the molar ratio of the reducing agent or the reducing agent solution in the reducing agent to the high-valence chromium is preferably 0.1-10: 1, more preferably 0.5 to 5: 1.
The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst disclosed by the invention is characterized in that the auxiliary agent is preferably one or more of nitrates or acetates of Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe and Zn.
The preparation method of the low-carbon alkane dehydrogenation microsphere catalyst, disclosed by the invention, comprises the following steps of:
adding water, alumina sol and pseudo-boehmite into a reactor heated in a water bath, and uniformly stirring; the weight ratio of aluminum to aluminum is 0.05-0.60: 1, acidifying with inorganic acid, heating to 45-90 ℃, and aging for 0.5-4 h; and cooling, adding macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 450-800 ℃ for 1-7 h to obtain the alumina microsphere carrier.
The preparation method of the low-carbon alkane dehydrogenation microspherical 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 microsphere catalyst prepared by the invention has the advantages that 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 carbon deposition resistance 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: the dehydrogenation catalyst carrier is alumina microsphere and is prepared by a spray drying method. Dissolving a high-valence chromium precursor in a reducing agent or a reducing agent solution, soaking the precursor in an alumina microsphere 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 the prepared catalyst2O3The content of (A) is 3-20 wt.%, and the content of the auxiliary agent is 0.5-6 wt.%.
The carrier component comprises macroporous alumina with the weight content of 30-80% and inorganic oxide binder with the weight content of 20-70%.
The macroporous alumina has a pseudo-boehmite structure, a boehmite structure or a gibbsite structure, and preferably alumina having a pseudo-boehmite or boehmite structure. The content of sodium oxide in the macroporous alumina is less than or equal to 0.3 percent and the content of silicon dioxide is less than or equal to 0.3 percent, calculated by 100 percent of the mass of the macroporous alumina; the pore volume of the macroporous alumina is 0.7-1.4 ml/g, preferably 0.8-1.2 ml/g.
The inorganic oxide binder is selected from one or a mixture of two of aluminum sol and pseudo-boehmite, preferably the mixture of the aluminum sol and the pseudo-boehmite, and when the inorganic oxide binder is the mixture of the aluminum sol and the pseudo-boehmite, the mass ratio of the alumina from the pseudo-boehmite to the alumina from the aluminum sol is preferably 1: 1-5: 1.
the dehydrogenation catalyst carrier is prepared by the following method:
⑴ adding metered water in a reactor heated in a water bath, wherein the amount of the water is 3-6 times of that of the dry basis;
⑵ adding aluminum sol and pseudo-boehmite, stirring uniformly, and adding the two matrix materials in no strict order;
⑶ acidifying with inorganic acid (hydrochloric acid or nitric acid) with aluminum acid weight ratio of 0.05-0.60 to peptize solid components in the binder;
⑷, heating to 45-90 ℃, and aging for 0.5-4 h;
⑸ cooling to room temperature, adding macroporous alumina, and adding macroporous alumina after adding inorganic acid into the binder solid component;
⑹, spray drying and forming after uniformly mixing, and roasting for 1-7 h at 450-800 ℃ to obtain the microsphere catalyst carrier.
The high-valence chromium is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4、K2CrO4One or more of (a).
The reducing agent 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 is preferably ethylene glycol and the reducing agent solution is preferably an aqueous glucose solution. 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 molar ratio of the reducing agent to the high-valence chromium in the reducing agent solution is 0.1-10, preferably 0.5-5.
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 is used for catalytic dehydrogenation of alkane components of C3-C6.
Reaction of high-valence Cr with reductant or reductant solution 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 microsphere carrier is effectively regulated and controlled, so that the activity, selectivity and stability of the catalyst are correspondingly improved.
Example 1
Adding 5kg of water, 0.4kg of pseudo-boehmite and 0.3kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying with 0.1kg of hydrochloric acid (analytically pure), heating to 50 ℃, and aging for 0.5 h; cooling to room temperature, adding 0.8kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 450 ℃ for 2h to obtain the microsphere carrier.
2.23g(NH4)2Cr2O7Dissolved in 8ml of ethylene glycol and impregnated in an equal volume to 10g of the microspheroidal support. Placing in an oven at 120 deg.C for 4 hr, washing with deionized water, filtering, and drying at 80 deg.C for 2 hr. 0.37g KNO3Dissolving in 8ml deionized water, soaking in the treated microsphere carrier in the same volume, drying at 80 deg.C for 4 hr, and calcining at 680 deg.C for 5 hr to obtain catalyst A.
Comparative example 1
Adding 5kg of water, 0.4kg of pseudo-boehmite and 0.3kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying with 0.1kg of hydrochloric acid (analytically pure), heating to 50 ℃, and aging for 0.5 h; cooling to room temperature, adding 0.8kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 450 ℃ for 2h to obtain the microsphere carrier.
7.08g Cr(NO3)3·9H2O、0.37g KNO3Dissolving in 4ml deionized water, soaking in 10g microsphere carrier in the same volume, drying at 80 deg.C for 4 hr, and calcining at 680 deg.C for 5 hr to obtain catalyst B.
Example 2
Adding 5kg of water, 0.3kg of pseudo-boehmite and 0.1kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying with 0.2kg of hydrochloric acid (analytically pure), heating to 70 ℃, and aging for 2 h; cooling to room temperature, adding 0.8kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 550 ℃ for 4 hours to obtain the microsphere carrier.
1.77g CrO3、2.48g(NH4)2C2O4Dissolved in 8ml of deionized water and impregnated in an equal volume to 10g of the microspheroidal support. Placing in an oven at 60 deg.C for 6h, washing with deionized water, filtering, and drying at 100 deg.C for 2 h. 0.78g Cu (NO)3)2·3H2O、1.12g Fe(NO3)3·9H2Dissolving O in 7ml deionized water, soaking the solution in the treated microsphere carrier in the same volume, drying at 120 ℃ for 3h, and roasting at 700 ℃ for 6h to obtain the catalyst which is marked as catalyst C.
Comparative example 2
Adding 5kg of water, 0.3kg of pseudo-boehmite and 0.1kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying with 0.2kg of hydrochloric acid (analytically pure), heating to 70 ℃, and aging for 2 h; cooling to room temperature, adding 0.8kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 550 ℃ for 4 hours to obtain the microsphere carrier.
7.08g Cr(NO3)3·9H2O、0.78g Cu(NO3)2·3H2O、1.12g Fe(NO3)3·9H2Dissolving O in 3.5ml deionized water, soaking in 10g microsphere carrier in the same volume, drying at 80 deg.C for 4 hr, and calcining at 700 deg.C for 6 hr to obtain catalyst D.
Example 3
Adding 5kg of water, 0.4kg of pseudo-boehmite and 0.1kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying by 0.3kg of nitric acid (analytically pure), heating to 80 ℃, and aging for 4 hours; cooling to room temperature, adding 0.5kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 700 ℃ for 6 hours to obtain the microsphere carrier.
1.30g K2Cr2O7Dissolved in 8ml glycerol and dipped in an equal volume into 10g of microsphere carrier. Placing in an oven at 140 deg.C for 1h, washing with deionized water, filtering, and drying at 80 deg.C for 4 h. 0.33g NaNO3、0.82g Ni(NO3)2·6H2Dissolving O in 8ml deionized water, soaking in the treated microsphere carrier in the same volume, drying at 60 deg.C for 6 hr, and calcining at 720 deg.C for 4 hr to obtain catalyst E.
Comparative example 3
Adding 5kg of water, 0.4kg of pseudo-boehmite and 0.1kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying by 0.3kg of nitric acid (analytically pure), heating to 80 ℃, and aging for 4 hours; cooling to room temperature, adding 0.5kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 700 ℃ for 6 hours to obtain the microsphere carrier.
3.54g Cr(NO3)3·9H2O、0.33g NaNO3、0.82g Ni(NO3)2·6H2Dissolving O in 6.0ml deionized water, soaking in 10g microsphere carrier in the same volume, drying at 80 deg.C for 4 hr, and calcining at 720 deg.C for 4 hr to obtain catalyst F.
Example 4
Adding 5kg of water, 0.3kg of pseudo-boehmite and 0.2kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying with 0.2kg of nitric acid (analytically pure), heating to 75 ℃, and aging for 3.5 h; cooling to room temperature, adding 0.6kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 800 ℃ for 3h to obtain the microsphere carrier.
2.30g Na2CrO40.39g of glucose was dissolved in 8ml of deionized water and the solution was immersed in an equal volume of 10g of the microsphere carrier. Placing in an oven at 85 deg.C for 4h, washing with deionized water, filtering, and drying at 95 deg.C for 3 h. 0.37g KNO3、0.32g La(NO3)3·6H2O、1.14g Fe(NO3)2·9H2Dissolving O in 7ml deionized water, soaking in the treated microsphere carrier in the same volume, drying at 70 deg.C for 5 hr, and calcining at 690 deg.C for 6 hr to obtain catalyst G.
Comparative example 4
Adding 5kg of water, 0.3kg of pseudo-boehmite and 0.2kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying with 0.2kg of nitric acid (analytically pure), heating to 75 ℃, and aging for 3.5 h; cooling to room temperature, adding 0.6kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 800 ℃ for 3h to obtain the microsphere carrier.
5.66g Cr(NO3)3·9H2O、0.37g KNO3、0.32g La(NO3)3·6H2O、1.14g Fe(NO3)2·9H2Dissolving O in 4.8ml deionized water, soaking in 10g microsphere carrier in the same volume, drying at 80 deg.C for 4 hr, and calcining at 690 deg.C for 6 hr to obtain catalyst, which is denoted as catalyst H.
Example 5
Adding 5kg of water, 0.25kg of pseudo-boehmite and 0.25kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying by 0.15kg of nitric acid (analytically pure), heating to 60 ℃, and aging for 3 h; cooling to room temperature, adding 0.5kg of macroporous alumina, uniformly mixing, spray drying, forming, and roasting at 750 ℃ for 3h to obtain the microsphere carrier.
3.77g K2CrO42.82g ascorbic acid was dissolved in 8ml deionized water and the same volume was immersed in 10g microsphere carrier. Placing in an oven at 60 deg.C for 1h, washing with deionized water, filtering, and drying at 80 deg.C for 4 h. 0.28g KNO3、0.65g Cu(NO3)2·3H2Dissolving O in 8ml deionized water, soaking the solution in the treated microsphere carrier in the same volume, drying at 60 deg.C for 6h, and calcining at 720 deg.C for 4h to obtain catalyst I.
Comparative example 5
Adding 5kg of water, 0.25kg of pseudo-boehmite and 0.25kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying by 0.15kg of nitric acid (analytically pure), heating to 60 ℃, and aging for 3 h; cooling to room temperature, adding 0.5kg of macroporous alumina, uniformly mixing, spray drying, forming, and roasting at 750 ℃ for 3h to obtain the microsphere carrier.
7.79g Cr(NO3)3·9H2O、0.28g KNO3、0.65g Cu(NO3)2·3H2Dissolving O in 3.0ml deionized water, soaking in 10g of microsphere carrier in the same volume, drying at 80 deg.C for 4h, and calcining at 720 deg.C for 4h to obtain catalyst, denoted as catalyst J.
Example 6
Adding 5kg of water, 0.35kg of pseudo-boehmite and 0.2kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying with 0.2kg of nitric acid (analytically pure), heating to 60 ℃, and aging for 2.5 h; cooling to room temperature, adding 0.55kg of macroporous alumina, uniformly mixing, spray drying, forming, and roasting at 650 ℃ for 5 hours to obtain the microsphere carrier.
3.23g(NH4)2CrO4Dissolved in 8ml of ethylene glycol and impregnated in an equal volume to 10g of the microspheroidal support. Placing in an oven at 150 deg.C for 0.5h, washing with deionized water, filtering, and drying at 80 deg.C for 2 h. 0.28g KNO3、0.65g Cu(NO3)2·3H2Dissolving O in 8ml deionized water, soaking the obtained product in the treated microsphere carrier in the same volume, drying at 80 ℃ for 4h, and roasting at 680 ℃ for 8h to obtain the catalyst, namely the catalyst K.
Comparative example 6
Adding 5kg of water, 0.35kg of pseudo-boehmite and 0.2kg of alumina sol into a reactor heated in a water bath, uniformly stirring, acidifying with 0.2kg of nitric acid (analytically pure), heating to 60 ℃, and aging for 2.5 h; cooling to room temperature, adding 0.55kg of macroporous alumina, uniformly mixing, spray drying, forming, and roasting at 650 ℃ for 5 hours to obtain the microsphere carrier.
3.23g(NH4)2CrO4、0.28g KNO3、0.65g Cu(NO3)2·3H2Dissolving O in 7.6ml deionized water, soaking the solution in the treated microsphere carrier in the same volume, drying at 80 ℃ for 4h, and roasting at 680 ℃ for 8h to obtain a catalyst, namely a catalyst L.
Example 7
Adding 5kg of water and 0.5kg of pseudo-boehmite into a reactor heated in a water bath, uniformly stirring, acidifying by 0.2kg of nitric acid (analytically pure), heating to 60 ℃, and aging for 2.5 h; cooling to room temperature, adding 0.5kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 650 ℃ for 5 hours to obtain the microsphere carrier.
1.66g(NH4)2Cr2O7、1.63g Na2CrO40.92g of glucose was dissolved in 8ml of deionized water and the solution was immersed in an equal volume of 10g of the microsphere carrier. Placing in an oven at 95 deg.C for 2h, washing with deionized water, filtering, and drying at 60 deg.C for 10 h. 0.16g Ca (NO)3)2·4H2O、0.11g Sr(NO3)2、2.33g Co(NO3)2·6H2Dissolving O in 7ml deionized water, soaking the solution in the treated microsphere carrier in the same volume, drying at 80 ℃ for 4h, roasting at 750 ℃ for 10h, and molding and screening to obtain the catalyst, namely the catalyst M.
Comparative example 7
Adding 5kg of water and 0.5kg of pseudo-boehmite into a reactor heated in a water bath, uniformly stirring, acidifying by 0.2kg of nitric acid (analytically pure), heating to 60 ℃, and aging for 2.5 h; cooling to room temperature, adding 0.5kg of macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 650 ℃ for 5 hours to obtain the microsphere carrier.
9.3g Cr(NO3)3·9H2O、0.16g Ca(NO3)2·4H2O、0.11g Sr(NO3)2、2.33g Co(NO3)2·6H2Dissolving O in 3.8ml deionized water, soaking in 10g microsphere carrier in equal volume, drying at 80 deg.C for 4 hr, calcining at 750 deg.C for 10 hr, molding, and sievingCatalyst is designated catalyst N.
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.
TABLE 1 evaluation of the Activity of the catalyst
Figure GDA0002336142270000111
As can be seen from table 1, the catalyst (A, C, E, G, I, K, M) synthesized using in situ reduction is 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 (13)

1. A preparation method of a low-carbon alkane dehydrogenation microspherical catalyst comprises the following steps: dissolving a precursor of high-valence chromium in a reducing agent or a reducing agent solution, then soaking the precursor into an alumina microsphere carrier, reacting at the reaction temperature of 30-200 ℃ for 0.5-20 h, then washing, filtering and drying, soaking an auxiliary agent, and drying and roasting to obtain a catalyst;
the alumina microsphere carrier comprises macroporous alumina with the weight content of 30-80% and an inorganic oxide binder with the weight content of 20-70%;
the reducing agent is glycol and glycerol, and the reducing agent solution is an aqueous solution of glucose, oxalic acid or ascorbic acid components.
2. The method of preparing a lower alkane dehydrogenation microspherical catalyst of claim 1, wherein the macroporous alumina has a pseudo-boehmite structure, a monohydrate bauxite structure, or a gibbsite structure.
3. The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst as recited in claim 1, wherein the content of sodium oxide in the macroporous alumina is less than or equal to 0.3 percent, and the content of silicon dioxide in the macroporous alumina is less than or equal to 0.3 percent, based on 100 percent of the mass of the macroporous alumina; the pore volume of the macroporous alumina is 0.7-1.4 ml/g.
4. The method for preparing the microsphere catalyst for dehydrogenating light alkane according to claim 1, wherein the inorganic oxide binder is alumina sol and/or pseudo-boehmite.
5. The method for preparing the low-carbon alkane dehydrogenation microspherical catalyst of claim 4, wherein when the inorganic oxide binder is a mixture of aluminum sol and pseudo-boehmite, the mass ratio of the alumina from the pseudo-boehmite to the alumina from the aluminum sol is 1: 1-5: 1.
6. the method of claim 1, wherein the precursor of high valence chromium is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4One or more of them.
7. The method for preparing the low-carbon alkane dehydrogenation microsphere catalyst according to claim 1, wherein the mass concentration of the glucose, oxalic acid or ascorbic acid component is 1 wt.% to 60 wt.%.
8. The method for preparing the low-carbon alkane dehydrogenation microsphere catalyst according to claim 7, wherein the mass concentration of the glucose, oxalic acid or ascorbic acid component is 3 wt.% to 30 wt.%.
9. The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst as defined in any one of claims 1-8, wherein the molar ratio of the reducing agent to the high-valence chromium is 0.1-10: 1.
10. the preparation method of the low-carbon alkane dehydrogenation microspherical catalyst of claim 9, wherein the molar ratio of the reducing agent to the high-valence chromium is 0.5-5: 1.
11. The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst of any one of claims 1 to 8, 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.
12. The method for preparing the low-carbon alkane dehydrogenation microspherical catalyst of claim 5, wherein the alumina microspherical support is prepared by the following method:
adding water, alumina sol and pseudo-boehmite into a reactor heated in a water bath, and uniformly stirring; the weight ratio of aluminum to aluminum is 0.05-0.60: 1, acidifying with inorganic acid, heating to 45-90 ℃, and aging for 0.5-4 h; and cooling, adding macroporous alumina, uniformly mixing, spray-drying, forming, and roasting at 450-800 ℃ for 1-7 h to obtain the alumina microsphere carrier.
13. The preparation method of the low-carbon alkane dehydrogenation microspherical catalyst as claimed in any one of claims 1 to 8, 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 ℃.
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