CN112973771B - Spherical catalyst carrier containing molecular sieve and alumina, preparation and application thereof - Google Patents

Spherical catalyst carrier containing molecular sieve and alumina, preparation and application thereof Download PDF

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CN112973771B
CN112973771B CN202110207677.2A CN202110207677A CN112973771B CN 112973771 B CN112973771 B CN 112973771B CN 202110207677 A CN202110207677 A CN 202110207677A CN 112973771 B CN112973771 B CN 112973771B
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sol
molecular sieve
catalyst carrier
pellets
spherical catalyst
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CN112973771A (en
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韩伟
潘相米
梁衡
艾珍
吴砚会
李南锌
李扬
何霖
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Southwest Research and Desigin Institute of Chemical Industry
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a spherical catalyst carrier containing a molecular sieve and alumina, belonging to the technical field of catalysts. The catalyst carrier is prepared by precipitating and acidifying inorganic aluminum salt by ammonia water to obtain sol, adding a mixed solution of ball-milled pseudo-boehmite and a molecular sieve and a sol modification auxiliary agent into the sol, then dropping the sol in an oil ammonia column, molding and aging, and finally washing, drying and calcining the sol to obtain the composite microspheres with high strength and large specific surface. The invention also provides a preparation method and application of the spherical catalyst carrier. The invention mixes the slurry obtained by ball milling pseudo-boehmite and molecular sieve with dilute sol and then peptizes the mixture again to obtain sol in which the molecular sieve and alumina particles are uniformly dispersed; the sol modifier is added into the sol to ensure that the sol is more stable, the microscopic particles of the formed sphere are more uniformly distributed, and the sphericity is better. When the spherical catalyst carrier is used for preparing the low-carbon alkane dehydrogenation catalyst, the dehydrogenation activity, the olefin selectivity and the carbon deposition resistance are good.

Description

Spherical catalyst carrier containing molecular sieve and alumina, preparation and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a spherical catalyst carrier containing a molecular sieve and alumina, and preparation and application thereof.
Background
The technology for preparing olefin by dehydrogenation of small molecular saturated hydrocarbon is industrialized as early as 30 s in the 20 th century, but due to the development of oil refining technology after the second war, the propylene as a byproduct of steam cracking is enough to meet the market demand, so that the technical route of alkane dehydrogenation is not regarded as important. Over the last decade, with the rapid development of the shale gas industry all over the world, the condensate liquid by-produced by the shale gas industry provides a large amount of cheap ethane and propane resources all over the world, and simultaneously, the yield of petroleum is continuously improved, and the yield of propane in associated gas is also increasingly large. Therefore, attention is paid to the dehydrogenation technology of low-carbon alkane. The alkane dehydrogenation technology comprises three main types, namely anaerobic dehydrogenation, oxidative dehydrogenation and membrane reaction dehydrogenation. Oxidative dehydrogenation and membrane reaction dehydrogenation still have great difference from industrialization. The industrialized direct dehydrogenation process mainly comprises a fixed bed dehydrogenation process (Cr)2O3/Al2O3Catalyst), moving bed dehydrogenation process (Pt-Sn/Al)2O3A catalyst). Pt-Sn/gamma-Al2O3The dehydrogenation method is environment-friendly and has excellent dehydrogenation performance, systematic research has been carried out at home and abroad, a plurality of important achievements are obtained, and a plurality of research units apply for related dehydrogenation patents.
In existing industrial plants, Pt-Sn/gamma-Al2O3The catalyst is mainly used for the moving bed dehydrogenation process, and the catalyst carrier is spherical alumina, and the single strength is more than 30N per particle. Since the direct dehydrogenation reaction temperature is above 600 ℃, deep dehydrogenation of alkanes easily occurs to generate dienes or alkynes, which undergo further cyclopolymerization to form coke on the catalyst. These cokes accumulate as the reaction proceeds and decrease the catalytic activity, so the catalyst needs to be regenerated continuously; in addition, the excellent catalyst carrier can provide a proper microstructure to fully disperse the active components, thereby improving the catalytic performance. Thus, the modified element with good dispersion can be developedThe spherical carrier with excellent carbon deposition resistance is improved Pt-Sn/gamma-Al2O3One of the key directions for catalyst performance.
Disclosure of Invention
The invention aims to provide a spherical catalyst carrier, which is prepared by adopting an oil ammonia method and contains a molecular sieve and alumina.
The purpose of the invention is realized by the following technical scheme:
a spherical catalyst carrier containing a molecular sieve and alumina is prepared by precipitating inorganic aluminum salt with ammonia water and acidifying to obtain sol, adding a mixed solution of ball-milled pseudo-boehmite and the molecular sieve and a sol modification auxiliary agent into the sol, dropping the sol in an oil ammonia column, forming, aging, washing, drying and calcining to obtain the composite microspheres with high strength and large specific surface area.
Further, Al in the catalyst carrier2O3The content is 50-80%, and the content of the molecular sieve is 20-50%; the average sphere particle size of the catalyst carrier is 1.5-2.0 mm, the average strength is not less than 40N/particle, and the BET specific surface area is 200-300 m2(ii) per gram, the bulk specific gravity is 0.5-0.7 g/ml.
A method for preparing a spherical catalyst carrier containing a molecular sieve and alumina comprises the following steps:
1) dissolving inorganic aluminum salt in deionized water, adding ammonia water under a closed condition to control the pH value to be 7-8, and then filtering and washing for multiple times to obtain a wet filter cake; adding a proper amount of deionized water into the wet filter cake, uniformly stirring, adding an inorganic strong acid solution for peptizing, controlling the pH value of the sol to be 2.5-4.5, and controlling the solid content of a dry basis to be 20-40;
2) mixing macroporous pseudo-boehmite and a silicon-aluminum molecular sieve, adding deionized water for ball milling, wherein the total solid content of the pseudo-boehmite and the molecular sieve in a suspension after ball milling is 20-50%;
3) adding the turbid liquid obtained in the step 2) into the sol obtained in the step 1), then adding a sol modifier, uniformly mixing the substances, adding inorganic strong acid again under the stirring condition, and controlling the pH value of the solution to be 2.5-3.5;
4) forming the aluminum sol obtained in the step 3) in an oil ammonia column, wherein the upper layer of the oil ammonia column is an oil phase layer, and the lower layer of the oil ammonia column is a mixed solution of ammonia water and ammonium/amine salt;
5) and taking out the aged pellets, and sequentially washing, drying and calcining to obtain the composite pellets with high strength and large specific surface area.
Further, in the step 1), the inorganic aluminum salt is one or two of aluminum sulfate, aluminum nitrate and aluminum chloride; the mass concentration of the ammonia water is 5-10%, the inorganic strong acid is one of hydrochloric acid, nitric acid or perchloric acid, and the mass concentration of the inorganic strong acid is 15-65%.
Further, in the step 2), the peptization index of the macroporous pseudo-boehmite is 30-60, the pore volume is more than or equal to 0.5ml/g, and the mass of a dry basis is reduced by 30% after calcination at 300 ℃; the silicon-aluminum molecular sieve is one of ZSM-5, SPAO-34, H beta or mordenite.
Further, in the step 3), the sol modifier contains two substances, wherein one substance is one of urea and urotropine, and the mass of the sol modifier accounts for 5-10% of the dry basis weight of the sol; the other one is one of stearic acid amide emulsion, glycerol polyoxypropylene ether, glycerin monostearate and fatty alcohol emulsion, and the mass of the one accounts for 0.05-0.15% of the dry weight of the sol; the inorganic aluminum salt is one or two of aluminum sulfate, aluminum nitrate and aluminum chloride.
Further, in the step 4), the upper oil phase layer is one of straight-chain paraffin of C9-C15, gasoline, kerosene, paraffin and engine oil; and the ammonium/amine salt in the lower mixed solution is one of ammonium chloride, ammonium sulfate, ammonium nitrate and ethanolamine.
Further, in the step 4), the mass concentration of ammonia water in the lower layer mixed solution is 1% -5%, and the mass concentration of ammonium/amine salt is 5% -10%.
Further, the specific operation of step 5) is: and taking out the aged pellets, repeatedly washing with deionized water, drying overnight at 40-80 ℃, heating to 500-650 ℃ for 20-40 h, and calcining for 2-6 h to obtain the composite pellets with high strength and large specific surface area.
The application of a spherical catalyst carrier containing a molecular sieve and alumina in the preparation of a low-carbon alkane dehydrogenation catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention obtains slurry with highly fused alumina and molecular sieve by ball milling pseudo-boehmite and molecular sieve, mixes the slurry with dilute sol and then peptizes the mixture again to obtain a sol system with uniformly dispersed molecular sieve and alumina particles; the sol modifier with two components is added into the system, so that not only can the colloid be more stable, the distribution of microscopic particles of a formed sphere be more uniform, but also the sphericity of the sphere is better.
The molecular sieve-alumina spherical catalyst carrier prepared by the method is used as a carrier of a low-carbon alkane dehydrogenation catalyst, and the prepared catalyst is high in strength and good in wear resistance; the catalyst is used in the reaction process, and has the characteristics of good dehydrogenation activity, high selectivity of low-carbon olefin and strong anti-carbon performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
All of the features disclosed in this specification, or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification (including any accompanying claims, abstract) may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Hereinafter, "silicon-aluminum ratio" means SiO, unless otherwise specified2/Al2O3A molar ratio; the following percentages represent mass percentages unless otherwise specified; the solid-liquid ratio represents the proportional relation between the solid mass g and the liquid body mL.
Example 1
The preparation process of the spherical catalyst carrier containing the molecular sieve and the alumina in the embodiment is as follows:
1. dissolving 375g of aluminum nitrate in 500g of deionized water at 60 ℃, adding 7% ammonia water solution under a closed condition until the pH value is between 7 and 8, and then washing the solution under a filter pressing condition until the filtrate is neutral to obtain a wet filter cake; adding deionized water into the wet filter cake, uniformly stirring, adding a nitric acid solution with the concentration of 50% for peptizing, controlling the pH value of the sol to be 4.0, and finally controlling the solid content of the sol to be 35%;
2. 100g of macroporous pseudo-boehmite and 60g of ZSM-5 (silica-alumina ratio of 200) molecular sieve are mixed, deionized water is added for ball milling, the total solid content of the pseudo-boehmite and the molecular sieve in suspension after ball milling is 50%, and the particle D90 in the suspension after ball milling is 30 nm.
3. And (3) adding the suspension obtained in the step (2) into the sol obtained in the step (1), then adding 10g of urea and 0.2g of glyceryl monostearate, uniformly mixing under the condition of stirring rotation speed of 30r/min, adding a nitric acid solution with the concentration of 50%, and controlling the pH value of the solution to be 2.5.
4. And (3) forming the alumina sol obtained in the step (3) in an oil ammonia column, wherein the dropping speed is 30 drops/min, the aging time is 1h, the upper layer of the oil ammonia column is 30mm of heptane, the lower layer of the oil ammonia column is a mixed solution of ammonia water and ammonium nitrate with the height of 50cm, and the concentrations of the two are respectively 3% and 8%.
5. And taking out the aged pellets, repeatedly washing the pellets by deionized water, drying the pellets overnight at 60 ℃ under the condition of flowing air, heating the pellets to 600 ℃ for 25 hours, calcining the pellets for 4 hours to obtain the required spherical catalyst carrier, and sieving the spherical catalyst carrier between 1.5 and 2.1mm to obtain the spherical catalyst carrier with the average particle size of 1.93 mm.
Example 2
The preparation process of the spherical catalyst carrier containing the molecular sieve and the alumina in the embodiment is as follows:
1. dissolving 270g of aluminum nitrate in 500g of deionized water at the temperature of 80 ℃, adding 7% ammonia water solution under a closed condition until the pH value is 7-8, and then washing the solution under a filter pressing condition until the filtrate is neutral to obtain a wet filter cake; adding deionized water into the wet filter cake, uniformly stirring, adding a nitric acid solution with the concentration of 30% for peptizing, controlling the pH value of the sol to be 3.5, and finally, controlling the solid content of the sol to be 25%;
2. 80g of macroporous pseudo-boehmite and 70g of ZSM-5 (silica-alumina ratio 100) molecular sieve are mixed, and then deionized water is added for ball milling, so that the total solid content of the pseudo-boehmite and the molecular sieve in the suspension after ball milling is 35%, and the particle D90 in the suspension after ball milling is 25 nm.
3. And (3) adding the suspension obtained in the step (2) into the sol obtained in the step (1), then adding 15g of urea and 0.1g of glycerol polyoxypropylene ether, uniformly mixing under the condition of stirring speed of 60r/min, adding a nitric acid solution with the concentration of 30% again, and controlling the pH value of the solution to be 3.0.
4. And (3) forming the alumina sol obtained in the step (3) in an oil ammonia column, wherein the dropping speed is 45 drops/min, the aging time is 1.5h, the upper layer of the oil ammonia column is 15mm of paraffin, the lower layer of the oil ammonia column is a mixed solution of ammonia water and ethanolamine with the height of 30cm, and the concentrations of the two are 1% and 10% respectively.
5. And taking out the aged pellets, repeatedly washing the pellets by deionized water, drying the pellets overnight at 50 ℃ under the condition of flowing air, heating the pellets to 500 ℃ for 35 hours, calcining the pellets for 8 hours to obtain the required spherical catalyst carrier, and sieving the spherical catalyst carrier between 1.5 and 2.1mm to obtain the spherical catalyst carrier with the average particle size of 1.75 mm.
Example 3
The preparation process of the spherical catalyst carrier containing the molecular sieve and the alumina in the embodiment is as follows:
1. dissolving 150g of anhydrous aluminum chloride in 650g of deionized water at 50 ℃, adding 10% ammonia water solution under a closed condition until the pH value is between 7 and 8, and then washing the solution under a filter pressing condition until the filtrate is neutral to obtain a wet filter cake; adding deionized water into the wet filter cake, uniformly stirring, adding a nitric acid solution with the concentration of 40% for peptizing, controlling the pH value of the sol to be 3.0, and finally controlling the solid content of the sol to be 28%;
2. 150g of macroporous pseudo-boehmite and 80g of SPAO-34 (silica alumina ratio is 0.4) molecular sieve are mixed, and then deionized water is added for ball milling, so that the total solid content of the pseudo-boehmite and the molecular sieve in the suspension after ball milling is 40%, and the particle D90 in the suspension after ball milling is 18 nm.
3. And (3) adding the suspension obtained in the step (2) into the sol obtained in the step (1), then adding 10g of urotropine and 0.2g of fatty acid emulsion (HLB value 18), uniformly mixing under the condition of stirring rotation speed of 100r/min, adding a nitric acid solution with the concentration of 40% again, and controlling the pH value of the solution to be 3.2.
4. And (3) forming the alumina sol obtained in the step (3) in an oil ammonia column, wherein the dropping speed is 60 drops/min, the aging time is 0.5h, the upper layer of the oil ammonia column is kerosene with the thickness of 25mm, the lower layer of the oil ammonia column is a mixed solution of ammonia water and ammonium chloride with the height of 40cm, and the concentrations of the two are 5% and 5% respectively.
5. And taking out the aged pellets, repeatedly washing the pellets by deionized water, drying the pellets overnight at 80 ℃ under the condition of flowing air, heating the pellets to 550 ℃ for 40 hours, calcining the pellets for 5 hours to obtain the required spherical catalyst carrier, and sieving the spherical catalyst carrier between 1.5 and 2.1mm to obtain the spherical catalyst carrier with the average particle size of 1.86 mm.
Example 4
The preparation process of the spherical catalyst carrier containing the molecular sieve and the alumina in the embodiment is as follows:
1. dissolving 250g of aluminum nitrate in 480g of deionized water at 70 ℃, adding 6% ammonia water solution under a closed condition until the pH value is between 7 and 8, and then washing the solution under a filter pressing condition until the filtrate is neutral to obtain a wet filter cake; adding deionized water into the wet filter cake, uniformly stirring, adding concentrated hydrochloric acid for peptizing, controlling the pH value of the sol to be 2.5, and finally controlling the solid content of the sol to be 37%;
2. 120g of macroporous pseudo-boehmite and 50g of SPAO-34 (silica alumina ratio is 0.2) molecular sieve are mixed, and then deionized water is added for ball milling, so that the total solid content of the pseudo-boehmite and the molecular sieve in the suspension after ball milling is 25%, and the particle D90 in the suspension after ball milling is 22 nm.
3. And (3) adding the suspension obtained in the step (2) into the sol obtained in the step (1), then adding 9g of urotropine and 0.1g of stearic acid amide emulsion (with the solid content of 25%), uniformly mixing under the condition of stirring speed of 120r/min, adding concentrated hydrochloric acid again, and controlling the pH value of the solution to be 2.8.
4. Forming the alumina sol obtained in the step (3) in an oil ammonia column, wherein the dropping ball speed is 40 drops/min; the aging time was 3.0 h. The upper layer of the oil ammonia column is 50mm octane, the lower layer is a mixed solution of ammonia water and ammonium nitrate with the height of 60cm, and the concentrations of the two are respectively 2% and 6%.
5. And taking out the aged pellets, repeatedly washing with deionized water, drying overnight at 70 ℃ under the condition of flowing air, then heating to 500 ℃ for 30 hours, calcining for 2 hours to obtain the required pellets, and sieving between 1.5-2.1 mm to obtain the pellets with the average particle size of 2.05 mm.
Example 5
The preparation process of the spherical catalyst carrier containing the molecular sieve and the alumina in the embodiment is as follows:
1. dissolving 100g of aluminum nitrate in 200g of deionized water at 80 ℃, adding 8% ammonia water solution under a closed condition until the pH value is 7-8, and then washing the solution under a filter pressing condition until the filtrate is neutral to obtain a wet filter cake; adding deionized water into the wet filter cake, uniformly stirring, adding 30% perchloric acid for peptizing, and controlling the pH value of the sol to be 2.8, wherein the solid content of the sol is 20% finally;
2. 230g of macroporous pseudo-boehmite and 45g of ZSM-5 (silica-alumina ratio of 150) molecular sieve are mixed, and then deionized water is added for ball milling, so that the total solid content of the pseudo-boehmite and the molecular sieve in the suspension after ball milling is 35%, and the particle D90 in the suspension after ball milling is 10 nm.
3. And (3) adding the suspension obtained in the step (2) into the sol obtained in the step (1), then adding 15g of urea and 0.05g of fatty alcohol emulsion (HLB value 15), uniformly mixing under the condition of stirring rotation speed of 80r/min, adding 30% perchloric acid again for peptizing, and controlling the pH value of the solution to be 2.5.
4. And (3) forming the alumina sol obtained in the step (3) in an oil ammonia column, wherein the dropping speed is 50 drops/min, the aging time is 1.5h, the upper layer of the oil ammonia column is 10mm of engine oil, the lower layer of the oil ammonia column is 70cm high mixed solution of ammonia water and ammonium sulfate, and the concentrations of the two are respectively 4% and 8%.
5. And taking out the aged pellets, repeatedly washing the pellets by deionized water, drying the pellets overnight at 60 ℃ under the condition of flowing air, heating the pellets to 500 ℃ for 20 hours, calcining the pellets for 6 hours to obtain the required spherical catalyst carrier, and sieving the spherical catalyst carrier between 1.5 and 2.1mm to obtain the spherical catalyst carrier with the average particle size of 1.78 mm.
Example 6
The preparation process of the spherical catalyst carrier containing the molecular sieve and the alumina in the embodiment is as follows:
1. dissolving 180g of aluminum sulfate (18 g of water) in 450g of deionized water at 75 ℃, adding 10% ammonia water solution under a closed condition until the pH value is between 7 and 8, and then washing the solution under a filter pressing condition until the filtrate is neutral to obtain a wet filter cake; adding deionized water into the wet filter cake, uniformly stirring, adding 25% nitric acid for peptizing, controlling the pH value of the sol to be 4.5, and finally controlling the solid content of the sol to be 35%;
2. 50g of macroporous pseudo-boehmite and 50g of H beta (silica-alumina ratio 40) molecular sieve are mixed, and then deionized water is added for ball milling, so that the total solid content of the pseudo-boehmite and the molecular sieve in the suspension after ball milling is 28%, and the particle D90 in the suspension after ball milling is 15 nm.
3. And (3) adding the suspension obtained in the step (2) into the sol obtained in the step (1), then adding 11g of urea and 0.2g of stearic acid amide emulsion (solid content is 20%), uniformly mixing under the condition of stirring speed of 80r/min, adding 25% of nitric acid again for peptizing, and controlling the pH value of the solution to be 3.5.
4. And (3) forming the alumina sol obtained in the step (3) in an oil ammonia column, wherein the dropping speed is 35 drops/min, the aging time is 2.5h, the upper layer of the oil ammonia column is gasoline of 40mm, the lower layer of the oil ammonia column is a mixed solution of ammonia water and ammonium chloride with the height of 60cm, and the concentrations of the two are 3% and 10% respectively.
5. And taking out the aged pellets, repeatedly washing the pellets by deionized water, drying the pellets overnight at 75 ℃ under the condition of flowing air, heating the pellets to 650 ℃ for 40 hours, calcining the pellets for 2 hours to obtain the required spherical catalyst carrier, and sieving the spherical catalyst carrier between 1.5 and 2.1mm to obtain the spherical catalyst carrier with the average particle size of 1.61 mm.
Example 7
The preparation of the spherical catalyst support containing molecular sieve and alumina in this example is as follows:
1. dissolving 400g of aluminum nitrate in 850g of deionized water at 65 ℃, adding 6% ammonia water solution under a closed condition until the pH value is 7-8, and then washing the solution under a filter pressing condition until the filtrate is neutral to obtain a wet filter cake; adding deionized water into the wet filter cake, uniformly stirring, adding concentrated nitric acid for peptizing, controlling the pH value of the sol to be 3.0, and finally controlling the solid content of the sol to be 40%;
2. 60g of macroporous pseudo-boehmite and 40g of SPAO-34 (silica alumina ratio: 0.5) molecular sieve are mixed, and then deionized water is added for ball milling, so that the total solid content of the pseudo-boehmite and the molecular sieve in the suspension after ball milling is 25%, and the particle D90 in the suspension after ball milling is 18 nm.
3. And (3) adding the suspension obtained in the step (2) into the sol obtained in the step (1), then adding 10g of urotropine and 0.08g of glycerol polyoxypropylene ether, uniformly mixing under the condition of stirring speed of 90r/min, adding concentrated nitric acid again for peptization, and controlling the pH value of the solution to be 3.1.
4. And (3) forming the alumina sol obtained in the step (3) in an oil ammonia column, wherein the dropping ball speed is 40 drops/min, the aging time is 2.0h, the upper layer of the oil ammonia column is 30mm of engine oil, the lower layer of the oil ammonia column is a mixed solution of ammonia water and ammonium nitrate with the height of 40cm, and the concentrations of the two are 5% and 6% respectively.
5. And taking out the aged pellets, repeatedly washing the pellets by deionized water, drying the pellets overnight at 70 ℃ under the condition of flowing air, heating the pellets to 550 ℃ for 35 hours, calcining the pellets for 4 hours to obtain the required spherical catalyst carrier, and sieving the spherical catalyst carrier between 1.5 and 2.1mm to obtain the spherical catalyst carrier with the average particle size of 1.65 mm.
Example 8
The preparation process of the spherical catalyst carrier containing the molecular sieve and the alumina in the embodiment is as follows:
1. dissolving 200g of aluminum nitrate in 450g of deionized water at 70 ℃, adding 8% ammonia water solution under a closed condition until the pH value is 7-8, and then washing the solution under a filter pressing condition until the filtrate is neutral to obtain a wet filter cake; adding metered deionized water into the wet filter cake, uniformly stirring, adding 45% nitric acid for peptizing, controlling the pH value of the sol to be 3.8, and finally controlling the solid content of the sol to be 22%;
2. 120g of macroporous pseudo-boehmite and 35g of MOR (silica-alumina ratio of 35) molecular sieve are mixed, and then metered deionized water is added for ball milling, so that the total solid content of the pseudo-boehmite and the molecular sieve in the suspension after ball milling is 45%, and the particle D90 in the suspension after ball milling is 29 nm.
3. And (3) adding the suspension obtained in the step (2) into the sol obtained in the step (1), then adding 15g of urea and 0.2g of glyceryl monostearate, uniformly mixing under the condition of stirring rotation speed of 50r/min, adding 45% nitric acid again for peptizing, and controlling the pH value of the solution to be 2.6.
4. Forming the alumina sol obtained in the step 3 in an oil ammonia column, wherein the dropping ball speed is 55 drops/min; the aging time was 4.0 h. The upper layer of the oil ammonia column is 45mm octane, the lower layer is a mixed solution of 50cm high ammonia water and ethanolamine, and the concentration of the two is 4% and 8%.
5. And taking out the aged pellets, repeatedly washing the pellets by deionized water, drying the pellets overnight at 65 ℃ under the condition of flowing air, then heating the pellets to 600 ℃ for 30 hours, calcining the pellets for 2 hours to obtain the required spherical catalyst carrier, and sieving the spherical catalyst carrier between 1.5 and 2.1mm to obtain the spherical catalyst carrier with the average particle size of 1.82 mm.
Example 9
The preparation process of the spherical catalyst carrier containing the molecular sieve and the alumina in the embodiment is as follows:
weighing the chloroplatinic acid, the stannic chloride and the sodium chloride or the lithium chloride which are measured in sequence, mixing the chloroplatinic acid, the stannic chloride and the sodium chloride or the lithium chloride together, adding the mixture into the weighed distilled water, and fully stirring the mixture to dissolve the mixture.
100g of the spherical catalyst carrier prepared in example 1 was immersed in the above solution in an equal volume for 6 hours, then dried overnight at 120 ℃ and finally calcined at 550 ℃ for 4 hours to obtain example 9, the contents of active components are shown in Table 2.
Examples 10 to 13
The spherical catalyst carriers prepared in example 2, example 5, example 6 and example 8 were used as carriers in this order, and the same preparation method as in example 9 was used, except that the active component contents were different, which are shown in table 2.
Comparative example 1
The preparation method is basically the same as that of the embodiment 2, except that no ZSM-5 molecular sieve is added in the step 2, and the average grain diameter is 1.85mm after the sieving is carried out between 1.5 mm and 2.1 mm.
Comparative example 2
Referring to example 5, except that step 1 was not included, and the content of large-pore pseudo-boehmite in step 2 was 250g, without ball milling; the other steps are the same as the example 5, and the average grain diameter is 1.75mm after sieving the mixture between 1.5 mm and 2.1 mm.
Comparative example 3
Referring to example 8, except that only urea was added in step 3, a conventional oil ammonia column was used in step 4, and the lower layer was an 8% ammonia aqueous layer. The other steps are the same as the example 6, and the average grain diameter is 1.64mm after sieving the mixture between 1.5 mm and 2.1 mm.
Comparative examples 4 to 6
A catalyst was obtained by the same preparation method as in example 9, except that the contents of active components were different, using the spherical catalyst supports prepared in comparative examples 1 to 3 in this order, and the contents of active components are shown in Table 2.
Examples 9 to 13 and comparative examples 4 to 6 (catalysts prepared using the spherical catalyst supports prepared in comparative examples 1 to 3 as supports) were used for evaluation of propane dehydrogenation activity in a fixed bed micro-reactor: initial reaction temperature 605 deg.C, normal pressure, N2/H2/C3H8Is that 2: 1: 1, after 24h evaluation, the propane conversion and propylene selectivity are shown in Table 3.
TABLE 1 physicochemical Properties of catalyst supports prepared in examples 1 to 8 and comparative examples 1 to 3
Figure BDA0002951418920000121
Figure BDA0002951418920000131
TABLE 2 catalyst compositions for examples 9-13 and comparative examples 4-6
Figure BDA0002951418920000132
Table 3 activity data for catalysts of examples 9-13 and comparative examples 4-6 for propane dehydrogenation
Examples Propane conversion/%) Propylene selectivity/%)
Example 9 34.5 96.7
Example 10 35.6 93.4
Example 11 34.1 96.3
Example 12 32.3 95.2
Example 13 32.7 94.1
Comparative example 4 33.5 89.6
Comparative example 5 31.5 92.5
Comparative example 6 29.6 94.0
As can be seen from Table 1, the specific surface of the pellets prepared in comparative example 1 and comparative example 3 is significantly smaller, and the strength of the pellets prepared in comparative example 2 is lower than 40, which is difficult to meet the requirements of industrial application; the molecular sieve-alumina composite pellet prepared by the method has better strength (more than 40) and relatively larger specific surface (more than 200).
Meanwhile, as can be seen from table 3, the Pt-Sn-X modified catalyst prepared by using the spherical catalyst carrier prepared by the method of the present application as a carrier has good dehydrogenation activity when used for propane dehydrogenation; compared with examples 2, 5 and 8, the dehydrogenation activity of comparative examples 1 to 3 prepared by the same modification method is obviously reduced. In conclusion, the catalyst prepared by the spherical catalyst carrier containing the molecular sieve and the alumina is used for propane dehydrogenation, has excellent dehydrogenation performance and has industrial application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. A spherical catalyst carrier containing a molecular sieve and alumina is characterized in that inorganic aluminum salt is precipitated and acidified by ammonia water to obtain sol, mixed solution of ball-milled pseudo-boehmite and the molecular sieve and sol modification auxiliary agent are added into the sol, then dropping balls are formed and aged in an oil ammonia column, and finally washing, drying and calcining are carried out to obtain the spherical catalyst carrier with high strength and large specific surface areaThe composite pellet of (1); by mass percent, Al in the catalyst carrier2O3The content is 50-80%, and the content of the molecular sieve is 20-50%; the average sphere particle size of the catalyst carrier is 1.5-2.0 mm, the average strength is not less than 40N/particle, and the BET specific surface area is 200-300 m2(ii)/g, the bulk density is 0.5-0.7 g/mL; the molecular sieve is one of ZSM-5, SPAO-34, H beta or mordenite.
2. The method of claim 1, comprising the steps of:
1) dissolving inorganic aluminum salt in deionized water, adding ammonia water under a closed condition to control the pH value to be 7-8, and then filtering and washing for multiple times to obtain a wet filter cake; adding a proper amount of deionized water into the wet filter cake, uniformly stirring, adding an inorganic strong acid solution for peptizing, controlling the pH value of the sol to be 2.5-4.5, and controlling the solid content of a dry basis to be 20-40;
2) mixing macroporous pseudo-boehmite and a molecular sieve, adding deionized water for ball milling, wherein the total solid content of the pseudo-boehmite and the molecular sieve in suspension after ball milling is 20-50%;
3) adding the turbid liquid obtained in the step 2) into the sol obtained in the step 1), then adding a sol modifier, uniformly mixing the substances, adding inorganic strong acid again under the stirring condition, and controlling the pH value of the solution to be 2.5-3.5;
4) forming the aluminum sol obtained in the step 3) in an oil ammonia column, wherein the upper layer of the oil ammonia column is an oil phase layer, and the lower layer of the oil ammonia column is a mixed solution of ammonia water and ammonium/amine salt;
5) taking out the aged pellets, and sequentially washing, drying and calcining to obtain high-strength composite pellets with large specific surface area;
in the step 3), the sol modifier contains two substances, wherein one substance is one of urea and urotropine, and the mass of the sol modifier accounts for 5-10% of the dry basis weight of the sol; the other one is one of stearic acid amide emulsion, glycerol polyoxypropylene ether, glycerin monostearate and fatty alcohol emulsion, and the mass of the one is 0.05-0.15% of the dry basis weight of the sol.
3. The method of claim 2, wherein in the step 1), the inorganic aluminum salt is one or two of aluminum sulfate, aluminum nitrate and aluminum chloride; the mass concentration of the ammonia water is 5% -10%, the inorganic strong acid is one of hydrochloric acid, nitric acid or perchloric acid, and the mass concentration of the inorganic strong acid is 15% -65%.
4. The method for preparing the spherical catalyst carrier containing the molecular sieve and the alumina according to claim 2, wherein in the step 2), the peptization index of the macroporous pseudoboehmite is 30-60, the pore volume is not less than 0.5mL/g, and the mass of a dry base after calcination at 300 ℃ is reduced by 30%.
5. The method for preparing the spherical catalyst carrier containing the molecular sieve and the alumina according to claim 2, wherein in the step 4), the upper oil phase layer is one of linear alkanes of C9-C15, gasoline, kerosene, paraffin and engine oil; and the ammonium/amine salt in the lower mixed solution is one of ammonium chloride, ammonium sulfate, ammonium nitrate and ethanolamine.
6. The method for preparing the spherical catalyst carrier containing the molecular sieve and the alumina according to claim 2, wherein in the step 4), the mass concentration of the ammonia water in the lower mixed solution is 1% to 5%, and the mass concentration of the ammonium/amine salt is 5% to 10%.
7. The method for preparing the spherical catalyst carrier containing the molecular sieve and the alumina according to claim 2, wherein the step 5) is specifically performed by: and taking out the aged pellets, repeatedly washing the pellets by using deionized water, drying the pellets overnight at 40-80 ℃, and then heating the pellets to 500-650 ℃ for 20-40 h, and calcining the pellets for 2-6 h to obtain the composite pellets with high strength and large specific surface area.
8. Use of a spherical catalyst support comprising a molecular sieve and alumina, obtainable by a process according to any one of claims 2 to 7, in the preparation of a light alkane dehydrogenation catalyst.
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