WO2021066410A1 - Catalyseur pour l'ammoxydation de propylène, son procédé de préparation et procédé d'ammoxydation de propylène l'utilisant - Google Patents

Catalyseur pour l'ammoxydation de propylène, son procédé de préparation et procédé d'ammoxydation de propylène l'utilisant Download PDF

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WO2021066410A1
WO2021066410A1 PCT/KR2020/013098 KR2020013098W WO2021066410A1 WO 2021066410 A1 WO2021066410 A1 WO 2021066410A1 KR 2020013098 W KR2020013098 W KR 2020013098W WO 2021066410 A1 WO2021066410 A1 WO 2021066410A1
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catalyst
propylene
precursor
ammoxidation
formula
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PCT/KR2020/013098
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English (en)
Korean (ko)
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강경연
김지연
최준선
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주식회사 엘지화학
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Priority claimed from KR1020200123874A external-priority patent/KR102558452B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080006347.0A priority Critical patent/CN113164928A/zh
Priority to EP20872266.0A priority patent/EP3974058A4/fr
Priority to JP2021522080A priority patent/JP7161614B2/ja
Priority to US17/292,566 priority patent/US20220002233A1/en
Publication of WO2021066410A1 publication Critical patent/WO2021066410A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
    • C07C255/07—Mononitriles
    • C07C255/08—Acrylonitrile; Methacrylonitrile
    • 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

Definitions

  • the present invention relates to a catalyst for ammoxidation of propylene, a method for preparing the same, and a method for ammoxidation of propylene using the same.
  • the ammoxidation process of propylene is based on a reduction reaction of reacting ammonia and propylene and a mechanism of reoxidation by oxygen, the conversion rate of the reactant (i.e., propylene), and the selectivity of the reaction product (i.e., acrylonitrile). And catalysts of various compositions to increase the yield have been studied.
  • the catalyst having the secondary particle structure is vulnerable to friction, and may be deteriorated or damaged during the ammoxidation reaction of propylene in the fluidized bed reactor, and there is a disadvantage in that the catalyst must be continuously supplied.
  • the present invention provides a catalyst for ammoxidation of propylene having a uniform particle size distribution while being able to participate in the reaction as well as the outer surface portion (i.e., the surface of the catalyst) and the inner surface (pores) thereof. To prepare acrylonitrile in higher yield.
  • a catalyst for ammoxidation of propylene having a structure in which a metal oxide of a specific composition is supported on a silica carrier and having a uniform particle size distribution in the supported state is provided.
  • the catalyst of one embodiment may exhibit high catalytic efficiency and reactivity due to a large effective surface area capable of participating in the reaction, and may exhibit a small fine powder content and a uniform particle size distribution without a classification process.
  • FIG. 1 schematically shows a catalyst prepared using coprecipitation and spray drying.
  • first and second to be used hereinafter may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.
  • particle diameter Dv means a particle diameter at the v% point of the cumulative volume distribution according to the particle diameter. That is, D50 is the particle diameter at 50% of the cumulative volume distribution according to the particle diameter, D90 is the particle diameter at 90% of the cumulative volume distribution according to the particle diameter, and D10 is at 10% of the cumulative volume distribution according to the particle diameter. It is the particle size.
  • a metal oxide represented by the following Formula 1 is supported on a silica carrier; In a state in which the metal oxide is supported on a silica carrier, a D50 particle diameter of 30 to 300 ⁇ m, and a D10 particle diameter, a D50 particle diameter, and a D90 particle diameter satisfying the relationship of the following formula 1, provides a catalyst for ammoxidation of propylene. :
  • A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,
  • B is one or more elements of Li, Na, K, Rb, and Cs,
  • C is one or more elements of Cr, W, B, Al, Ca, and V, and
  • a to e, and x are the fractions of atoms or groups, respectively, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 2, and e is 0 to 10 , x is 24 to 48.
  • a generally known catalyst for ammoxidation of propylene is prepared through coprecipitation and spray drying, and is provided in a secondary particle structure in which metal oxide nanoparticles and silica nanoparticles are aggregated (FIG. 1).
  • the catalyst of the embodiment may be prepared by an impregnation method, and thus may be provided in a structure in which a metal oxide is supported on a silica carrier (FIG. 2).
  • a silica carrier may be immersed in a metal precursor solution prepared to satisfy a stoichiometric molar ratio of a desired metal oxide, and the metal precursor solution may be impregnated in the silica carrier.
  • the metal precursor remains on the pore walls of the silica carrier, and the metal precursor is oxidized in the firing process to form a film that continuously coats the pore walls of the silica carrier.
  • the catalyst of one embodiment thus prepared may have less fine powder content and superior durability than a catalyst prepared with the same composition through co-precipitation and spray drying, even if the classification process is not performed as a post-treatment after manufacture.
  • the catalyst of one embodiment is a catalyst by controlling the metal oxide composition to further include not only Mo and Bi known to increase the activity of the ammoxidation reaction, but also a metal forming an active point of an appropriate level for the ammoxidation reaction of propylene. It can further increase the activity.
  • the portion that can participate in the ammoxidation reaction of propylene by evenly supporting the metal oxide in the inner pores of the silica carrier is not only the outer surface portion (i.e., the surface of the catalyst) but also the inner surface (pore ), there is an advantage.
  • the catalyst of the embodiment may be implemented in a structure in which a metal oxide is supported on a silica carrier by using an impregnation method, has a small fine powder content and a uniform particle size distribution without a classification process.
  • the metal oxide exhibits excellent abrasion resistance due to the structure supported on the silica carrier and the uniform particle size distribution, so that acrylonitrile in a higher yield without additional supply of a catalyst during the ammoxidation reaction of propylene in the fluidized bed reactor. Can be manufactured.
  • the catalyst of the embodiment may include a silica carrier including second pores; An inner coating layer that continuously coats the walls of the second pores and includes a metal oxide represented by Chemical Formula 1; And first pores located inside the second pores and occupying an empty space excluding the inner coating layer.
  • the catalyst of the embodiment may have an egg-shell structure.
  • the silica carrier may include a non-porous core portion; And a porous shell portion positioned on the surface of the non-porous core and including second pores.
  • the porous shell includes a concave portion and a convex portion of a surface, and the concave portion has the second pores open to the surface of the porous shell. It may be formed.
  • the catalyst of the embodiment may include a coating layer that continuously coats the concave portions and the convex portions of the porous shell and includes a metal oxide represented by Chemical Formula 1; And first pores occupying an empty space excluding the coating layer in the concave portion of the silica carrier.
  • the catalyst of the embodiment may have a uniform particle size distribution compared to D50 and a small fine powder content in a state in which a metal oxide is supported on a silica support.
  • the catalyst of the embodiment may have a D50 particle diameter of 30 to 200 ⁇ m, and a ratio of the [difference between the D90 particle diameter and the D10 particle diameter] to the D50 particle diameter is less than 2.0, and may exhibit a narrow particle size distribution.
  • the catalyst of one embodiment has a lower limit of D50 particle size of 30 ⁇ m or more, 35 ⁇ m or more, 40 ⁇ m or more, or 45 ⁇ m or more, and an upper limit of 300 ⁇ m or less, 280 ⁇ m or less, 260 ⁇ m or less, 240 It can be made into ⁇ m or less, 220 ⁇ m or less, or 200 ⁇ m or less.
  • the catalyst of one embodiment has a ratio of [difference between D90 particle diameter and D10 particle diameter] to D50 particle diameter to be less than 2.0, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, or 1.5 or less, thereby providing a narrow particle size distribution. Can be indicated.
  • the uniformity of the particle size distribution represented by the catalyst of the embodiment may be supported by the fact that the D10 particle diameter and the D90 particle diameter relative to the D50 particle size satisfy the relationship of the following Equation 1, specifically the following Equation 1-1:
  • Particle wear refers to a phenomenon in which solid particles are decomposed through mechanical and chemical processes. Particle wear is classified into two types: abrasion and fragmentation, and both types may occur together.
  • catalyst particles may be worn and finely divided, and there is a need to make-up the catalyst by an amount that has been continuously worn, which may affect the economics of the entire process.
  • the ASTM9797-00 method is known as a standard for measuring the wear of particles. This is, after filling 50 g of catalyst (W0) in a vertical inner tube having an inner diameter of 35 mm and a height of 710 mm, and then flowing N 2 gas at 10 L/min, and after 5 hours, the amount of catalyst collected in the fine filter (W ) Is measured, and abrasion resistance (attrition loss) is measured using the following equation.
  • Abrasion resistance (attrition loss) (%) (W0)/W X 100
  • the catalyst of one embodiment has a wear resistance (attrition loss) measured according to the ASTM9797-00 method of 9% or less, 8.7% or less, 8.4% or less, 8.2% or less, or 8% or less, and the loss amount It is very small and can be excellent in abrasion resistance.
  • the catalyst of the embodiment exhibits excellent abrasion resistance, and even without additional supply of a catalyst during the ammoxidation reaction of propylene in the fluidized bed reactor, a higher yield It is possible to prepare acrylonitrile.
  • the active sites of the catalyst having insufficient or excessively high density for ammoxidation of propylene are formed. Can be.
  • the metal oxide is represented by the following Formula 1-1
  • the effect of increasing the conversion rate by increasing the rate of movement of the lattice oxygen of molybdenum of Fe, and the formation of a complex oxide with molybdenum of Co to increase the partial oxidation reaction characteristics of propylene As a synergistic effect of the effect, and the effect of increasing AN selectivity by dispersing the active point of the complex oxide containing molybdenum of K, the activity in the ammoxidation reaction of propylene may be higher:
  • a to d, and x are each an atom or a fraction of an atomic group, a is 0.1 to 5, specifically 0.1 to 2.0, b is 0.1 to 5, specifically 0.5 to 3.0 , c is 0.01 to 10, specifically 1 to 10, d is 0.01 to 2, specifically 0.01 to 1.0, x may be 24 to 48, specifically 28 to 45.
  • Metal oxide weight ratio of silica carrier
  • the catalyst of one embodiment is a weight ratio of 10:90 to 15:95, specifically 20:80 to 50:50, such as 15:85 to 35:65 of the metal oxide and the silica support (metal oxide: silica support) Can be included as.
  • the catalyst of the embodiment may have high selectivity of acrylonitrile with high activity.
  • a method of preparing the catalyst of the above-described embodiment is provided using an impregnation method.
  • the catalyst of one embodiment may be prepared through a series of processes in which a metal precursor solution is supported on the silica carrier using an impregnation method, dried and then calcined.
  • A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,
  • B is one or more elements of Li, Na, K, Rb, and Cs,
  • C is one or more elements of Cr, W, B, Al, Ca, and V, and
  • a to e, and x are the fractions of atoms or groups, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 2, and e is 0 to 10, x is 24 to 48.
  • the step of preparing the first precursor solution may be a step of dissolving water, a Mo precursor, and an additive at 20 to 80° C. to prepare an aqueous solution containing water, a Mo precursor, and an additive.
  • an additive including citric acid, oxalic acid, or a mixture thereof is used.
  • the additive functions as a strength control agent in the catalyst manufacturing process using coprecipitation and spray drying, but in one embodiment, the additive functions to make the first precursor solution transparent.
  • the weight ratio of the molybdenum precursor and the additive may satisfy 1:0.1 to 1:1, specifically 1:0.2 to 1:0.7, and the solubility of the molybdenum precursor increases within this range. It can be, but is not limited thereto.
  • a second precursor solution including the remaining metal precursors may be prepared.
  • the step of preparing the second precursor solution includes essentially a Bi precursor, an Fe precursor, an A precursor, and a B precursor in water at 20 to 50° C., and optionally, a C precursor (Cr, W, B , Al, Ca, and V may be to prepare a second precursor solution further comprising one or more elements).
  • the type of metal precursor other than the Mo precursor may be selected in consideration of the composition of the metal oxide in the final catalyst.
  • a second precursor solution including water, a Bi precursor, an Fe precursor, a Co precursor, and a K precursor may be prepared.
  • Processes of preparing the first and second precursor solutions are each independent, and the order of preparation is not limited.
  • first and second precursor solutions After mixing the first and second precursor solutions, they may be supported on a silica carrier.
  • the silica carrier including the aforementioned second pores is added to the mixture of the first and second precursor solutions, so that the mixture of the first and second precursor solutions is supported in the first pores in the silica support. I can.
  • the D50 size of the silica carrier on which the metal oxide is not supported may be 20 to 400 ⁇ m.
  • the silica carrier on which the metal oxide is not supported has a D50 size of 20 to 400 ⁇ m; It may include second pores having a diameter of 10 to 200 nm.
  • the D50 of the silica carrier itself without metal oxide has a lower limit of 20 ⁇ m or more, 25 ⁇ m or more, 30 ⁇ m or more, 35 ⁇ m or more, 40 ⁇ m or more, or 43 ⁇ m or more, and the upper limit is It may be 400 ⁇ m or less, 350 ⁇ m or less, 300 ⁇ m or less, 270 ⁇ m or less, 230 ⁇ m or less, or 200 ⁇ m or less.
  • the second pores contained in the silica carrier itself not carrying the metal oxide have a diameter of 10 nm or more, 15 nm or more, or 20 nm or more, and 200 nm or less, 100 nm or less, 50 nm or less, 40 It can be made into nm or less, or 30 nm or less.
  • Drying the silica carrier on which the mixture of the first and second precursor solutions is supported may include first vacuum drying the silica carrier on which the mixture of the first and second precursor solutions is supported at 120 to 160 mbar, and The first vacuum-dried material may be secondarily vacuum-dried at 30 to 50 mbar to obtain a silica carrier on which a mixture of the first and second precursor solutions is supported.
  • the first vacuum drying is performed at 60 to 80° C. for 1 to 2 hours, and the second vacuum drying is performed at 80 to 100° C. for 15 to 45 minutes, whereby the solvent (ie, water) is removed.
  • the solvent ie, water
  • the material on which the secondary vacuum drying has been completed can be fired immediately, but by tertiary drying at normal pressure, even the solvent (ie, water) remaining after the secondary vacuum drying can be effectively removed.
  • the third drying may be performed at 100 to 120 °C for 20 to 30 hours.
  • the solvent ie, water
  • the solvent there is no particular limitation as long as it is a drying condition capable of obtaining a carrier on which the first and second precursors are supported.
  • the dried material that is, the carrier on which the first and second precursors are supported, is calcined for 2 to 5 hours in a temperature range of 500 to 700° C. to finally obtain a catalyst.
  • drying and firing conditions are only examples, and a condition capable of sufficiently removing the solvent from the internal pores of the carrier and oxidizing the metal precursor is sufficient.
  • a method for ammoxidation of propylene comprising reacting propylene and ammonia in the presence of the catalyst of the above-described embodiment in a reactor.
  • the catalyst of the embodiment has high activity and stability at high temperature, and is used for ammoxidation reaction of propylene to increase the conversion rate of propylene, selectivity and yield of acrylonitrile.
  • Mo precursor solution 10.592 g of Mo precursor ((NH 4 ) 6 ⁇ Mo 7 O 24 ) and 0.1 g of citric acid were added and mixed in distilled water at 60° C. to prepare a Mo precursor solution.
  • the Mo precursor solution; And the Bi, Fe, Co, and K precursor mixture solution was mixed to complete a precursor mixture solution of Mo, Bi, Fe, Co, and K.
  • the total amount of distilled water is 36.59 g.
  • Silica (SiO 2 , D60-60A, AGC-Si) particles having a D50 particle diameter of 55 ⁇ m and an internal pore size of 24.4 nm were used as a carrier.
  • the silica carrier was added to the precursor mixture solution of Mo, Bi, Fe, Co, and K, and sequentially stirred at room temperature and 80° C. for 2 hours, respectively, and the Mo, Bi, Fe , Ni, Co, and K precursor mixture solution was sufficiently supported.
  • the silica carrier on which the precursor mixture solution of Bi, Fe, Co, and K is supported is recovered and introduced into a rotary vacuum dryer, followed by primary vacuum drying for 1 hour and 40 minutes under a pressure of 140 mbar and a temperature of 70° C. Then, a second vacuum drying was performed for 30 minutes under a pressure of 40 mbar and a temperature of 90°C.
  • Example 1 The material that has been completed until the second vacuum drying is recovered and put into an oven, and after 3 times drying for 24 hours under normal pressure and 110 °C temperature conditions, while maintaining the temperature of 580 °C in the box sintering furnace in an air atmosphere 3 hours During heat treatment, the catalyst of Example 1 was finally obtained.
  • the internal pressure of the reactor filled with the quartz fiber and the catalyst was maintained at atmospheric pressure (1 atm), and the internal temperature of the reactor was raised at a temperature increase rate of 10 °C/min, while nitrogen and ammonia gas were flowed as a pretreatment process. Accordingly, after the temperature inside the reactor reached 400° C., which is the temperature at which the ammoxidation reaction is possible, it was maintained in an atmosphere of reducing gas for 15 minutes to allow sufficient pretreatment.
  • a precursor solution was prepared according to the composition shown in Table 1 below, and the silica carriers shown in Table 2 were used, but the rest were the same as in Example 1 to prepare each of the catalysts of Examples 2 to 7.
  • each catalyst of Examples 2 to 7 was used to perform the ammoxidation process of flophyllene, and the product was recovered, and analysis was performed in the same manner as in Example 1.
  • Mo precursor ((NH 4 ) 6 Mo 7 O 24 ) and 3.18 g of citric acid were added and mixed in distilled water at 60° C. to prepare a Mo precursor solution.
  • silica sol silica sol 22.53 g (LUDOX AS 40, solid content: 40%) was added and stirred, and then a disk-type spray dryer was used. It was spray-dried at 120°C (inlet) and 230°C (outlet).
  • the catalyst of Comparative Example 1 was used instead of the catalyst of Example 1, and the ammoxidation process of flophyllene was performed in the same manner as in Example 1.
  • a precursor solution was prepared according to the composition shown in Table 1 below, and the silica carriers shown in Table 2 were used, but the rest of the catalysts of Comparative Examples 2 to 4 were prepared in the same manner as in Example 1.
  • Mo precursor ((NH 4 ) 6 ⁇ Mo 7 O 24 ) and 0.53 g of citric acid were added and mixed in distilled water at 60° C. to prepare a Mo precursor solution.
  • the Mo precursor solution; And the Bi, Co, Fe, Ni, K, Ce, Mg, and Rb precursor mixture solution was mixed to complete a precursor mixture solution of Mo, Bi, Fe, Co, and K.
  • the total amount of distilled water is 18.45 g.
  • Mo is (NH 4 ) 6 Mo 7 O 24
  • Bi is Bi(NO 3 ) 3 ⁇ 5H 2 O
  • Co is Co(NO 3 ) 2 ⁇ 6H 2 O
  • Fe is Fe( NO 3 ) 2 ⁇ 9H 2 O
  • K is KNO 3 .
  • the omitted unit is g.
  • Comparative Example 5 in which a number of substances were added to the dissimilar metal precursor solution was omitted from Table 1 for convenience.
  • Dv can be measured using a laser diffraction method. Specifically, each catalyst of Examples and Comparative Examples was introduced into a particle size measuring device (Microtrac, Blue wave) using a laser diffraction method, and the particle size distribution was calculated by measuring the difference in the diffraction pattern according to the particle size when the particles pass through the laser beam. do. In the measuring device, by calculating the particle diameter at the point where it becomes 10%, 50% and 90% of the cumulative volume distribution according to the particle diameter, the values of D10, D50 and D90 are obtained, and the particle size distribution ((D90-D10)/ The value of D50) can also be output.
  • a particle size measuring device Microtrac, Blue wave
  • Abrasion resistance Based on ASTM9797-00 method, after filling 50g of catalyst (W0) into a vertical inner tube with an inner diameter of 35mm and a height of 710mm, N2 gas flowed at 10L/min, and then collected in a fine filter after 5 hours. The amount of catalyst (W) was measured, and abrasion resistance was measured using the following equation.
  • the catalyst of the comparative example is prepared through coprecipitation and spray drying, and exhibits a wide particle size distribution such that a classification process is inevitable as a post-treatment.
  • the value of (D90-D10)/D50 is 2 or more.
  • the catalyst of the embodiment exhibits a uniform particle size distribution without a separate classification process as it is prepared through a series of processes in which a metal precursor solution is supported on a silica carrier and then a solvent is removed and then calcined.
  • the catalyst of Examples has a value of (D90-D10)/D50 of 1.5 or less, specifically 1.0 or less.
  • the catalyst of Comparative Example 1 as a result of being prepared through coprecipitation and spray drying, exhibits a wide particle size distribution such that post-treatment (eg, classification process) is inevitable.
  • post-treatment eg, classification process
  • the catalysts of Examples 1 to 7 were prepared through the impregnation method, they exhibited uniform particle size distribution without a separate classification process.
  • the catalysts of Comparative Examples 2 and 3 despite being prepared through the impregnation method, the D50 particle diameter does not satisfy the range (ie, 30 to 200 ⁇ m) specified in the above embodiment, and the particle size distribution and abrasion resistance are compared. It is inferior to Example 1.
  • the catalysts of Comparative Examples 4 and 5 were prepared through the impregnation method, and although the D50 particle diameter satisfies the range (ie, 30 to 200 ⁇ m) specified in the above embodiment, due to the effect of the active metal , Particle size distribution and abrasion resistance are equivalent to or inferior to Comparative Example 1.
  • the active metals included not only Mo and Bi, but also a plurality of active metals (i.e., Ce, Fe, Ni, Co, Mg, K, and Rb), the active ingredient was non-uniformly in the carrier. It is inferred that the particle size distribution and abrasion resistance remained at the same level as Comparative Example 1.
  • FID products such as ethylene (ehthlene), hydrogen cyanide, acetaldehyde, acetonitrile, and acetonitrile were analyzed, and as TCD , NH 3 , O 2 , Gas products such as CO and CO 2 and unreacted propylene were analyzed to determine the number of moles of propylene reacted and the number of moles of ammoxidation products in Examples and Comparative Examples, respectively.
  • the catalyst of Comparative Example 1 was prepared through coprecipitation and spray drying, and as a result, the internal pores were hardly included, so that the portion capable of participating in the reaction was limited to the outer surface portion.
  • the catalyst of Comparative Example 1 since the catalyst of Comparative Example 1 has a non-uniform particle size distribution, the catalyst efficiency and reactivity are low when the catalyst is applied to the ammoxidation process of propylene without classifying the catalyst. In addition, since the catalyst of Comparative Example 1 has a secondary particle structure that is vulnerable to friction, it may be deteriorated or damaged during the ammoxidation reaction of propylene in the fluidized bed reactor. Accordingly, the conversion rate of propylene and the yield of acrylonitrile are inevitably lowered unless additional catalysts are continuously supplied during the reaction.
  • the catalysts of Comparative Examples 2 to 5 have a particle size distribution and abrasion resistance equal to or inferior to Comparative Example 1, but have a larger effective surface area capable of participating in the reaction than Comparative Example 1 due to the structure manufactured by the impregnation method.
  • the conversion of propylene and the yield of acrylonitrile can be improved compared to Comparative Example 1.
  • the catalysts of Comparative Examples 2 and 3 do not satisfy the D50 particle diameter and particle size distribution (ie, D50 particle diameter: 30 to 200 ⁇ m, particle size distribution: (D90-D10)/D50 ⁇ 2.0) specified in the above embodiment.
  • the conversion rate of propylene and the yield of acrylonitrile are low compared to Examples 1 to 7.
  • the catalyst of Comparative Example 4 does not satisfy the particle size distribution (i.e., particle size distribution: (D90-D10)/D50 ⁇ 2.0) specified in the above embodiment, and contains only Mo and Bi as active metals. Under the influence of, the conversion rate of propylene and the yield of acrylonitrile are inferior to those of Examples 1 to 7.
  • the catalyst of Comparative Example 5 does not satisfy the particle size distribution (i.e., particle size distribution: (D90-D10)/D50 ⁇ 2.0) specified in the above embodiment, and as active metals, not only Mo and Bi, but also Ce, Fe, and Ni , Co, Mg, K, and Rb due to the influence of the formation of excessively dense active sites, the conversion of propylene and the yield of acrylonitrile are inferior to those of Examples 1 to 7.
  • the catalysts of Examples 1 to 7 not only have a larger effective surface area capable of participating in the reaction than Comparative Example 1 due to the structure prepared by the impregnation method, but also the D50 particle size and particle size distribution (i.e., D50 particle diameter: 30 to 200 ⁇ m, particle size distribution: (D90-D10)/D50 ⁇ 2.0), and the metal oxide composition satisfies the above formula (1), significantly improving the conversion rate of propylene and the yield of acrylonitrile It is evaluated as one.
  • D50 particle size and particle size distribution i.e., D50 particle diameter: 30 to 200 ⁇ m, particle size distribution: (D90-D10)/D50 ⁇ 2.0
  • the conversion of propylene and the yield of acrylonitrile were further adjusted by adjusting the D50 particle size and particle size distribution, and the metal oxide composition of the catalyst within the ranges specified in the above embodiment. It will also be possible to improve.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un catalyseur pour l'ammoxydation de propylène, son procédé de préparation et un procédé d'ammoxydation de propylène l'utilisant. Plus particulièrement, dans un mode de réalisation, la présente invention concerne un catalyseur ayant une structure dans laquelle un oxyde métallique est imprégné dans un support de silice, et ayant une distribution de taille de particules étroite et une excellente résistance à l'abrasion.
PCT/KR2020/013098 2019-09-30 2020-09-25 Catalyseur pour l'ammoxydation de propylène, son procédé de préparation et procédé d'ammoxydation de propylène l'utilisant WO2021066410A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202080006347.0A CN113164928A (zh) 2019-09-30 2020-09-25 用于丙烯的氨氧化催化剂、该催化剂的制造方法、使用所述催化剂的氨氧化方法
EP20872266.0A EP3974058A4 (fr) 2019-09-30 2020-09-25 Catalyseur pour l'ammoxydation de propylène, son procédé de préparation et procédé d'ammoxydation de propylène l'utilisant
JP2021522080A JP7161614B2 (ja) 2019-09-30 2020-09-25 プロピレンのアンモ酸化用触媒、その製造方法、それを用いたプロピレンのアンモ酸化方法
US17/292,566 US20220002233A1 (en) 2019-09-30 2020-09-25 Ammoxidation catalyst for propylene, manufacturing method of the same catalyst, ammoxidation method using the same catalyst

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR20190121172 2019-09-30
KR10-2019-0121172 2019-09-30
KR10-2019-0134089 2019-10-25
KR20190134089 2019-10-25
KR1020200123874A KR102558452B1 (ko) 2019-10-25 2020-09-24 프로필렌의 암모산화용 촉매, 이의 제조 방법, 이를 이용한 프로필렌의 암모산화 방법
KR10-2020-0123874 2020-09-24

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60166037A (ja) * 1984-02-07 1985-08-29 Nitto Chem Ind Co Ltd シリカ担持アンチモン含有酸化物触媒の製法
KR100687671B1 (ko) * 2003-03-05 2007-03-02 아사히 가세이 케미칼즈 가부시키가이샤 입상 다공성 암모산화 촉매
WO2011119203A1 (fr) * 2010-03-23 2011-09-29 Ineos Usa Llc Procédé d'ammoxydation à haut rendement, et catalyseurs à base de mélanges d'oxydes métalliques
KR101537459B1 (ko) * 2011-04-21 2015-07-16 아사히 가세이 케미칼즈 가부시키가이샤 실리카 담지 촉매
KR20160066922A (ko) * 2014-12-03 2016-06-13 주식회사 엘지화학 다성분계 복합금속산화물 촉매, 이의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60166037A (ja) * 1984-02-07 1985-08-29 Nitto Chem Ind Co Ltd シリカ担持アンチモン含有酸化物触媒の製法
KR100687671B1 (ko) * 2003-03-05 2007-03-02 아사히 가세이 케미칼즈 가부시키가이샤 입상 다공성 암모산화 촉매
WO2011119203A1 (fr) * 2010-03-23 2011-09-29 Ineos Usa Llc Procédé d'ammoxydation à haut rendement, et catalyseurs à base de mélanges d'oxydes métalliques
KR101537459B1 (ko) * 2011-04-21 2015-07-16 아사히 가세이 케미칼즈 가부시키가이샤 실리카 담지 촉매
KR20160066922A (ko) * 2014-12-03 2016-06-13 주식회사 엘지화학 다성분계 복합금속산화물 촉매, 이의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3974058A4 *

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