WO2021066410A1 - Catalyst for ammoxidation of propylene, method for preparing same, and method for ammoxidation of propylene using same - Google Patents
Catalyst for ammoxidation of propylene, method for preparing same, and method for ammoxidation of propylene using same Download PDFInfo
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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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- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 76
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 72
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000002245 particle Substances 0.000 claims abstract description 96
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 36
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims description 117
- 239000000203 mixture Substances 0.000 claims description 40
- 239000011148 porous material Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 229910052700 potassium Inorganic materials 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000012692 Fe precursor Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 40
- 238000005299 abrasion Methods 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 37
- 230000008569 process Effects 0.000 description 31
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000005470 impregnation Methods 0.000 description 14
- 229910052797 bismuth Inorganic materials 0.000 description 12
- 238000000975 co-precipitation Methods 0.000 description 11
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- 238000004458 analytical method Methods 0.000 description 9
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- 239000011163 secondary particle Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
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- 239000007789 gas Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 239000012695 Ce precursor Substances 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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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Abstract
The present invention relates to a catalyst for ammoxidation of propylene, a method for preparing same, and a method for ammoxidation of propylene using same. Specifically, provided in one embodiment of the present invention is a catalyst having a structure in which a metal oxide is impregnated in a silica carrier, and having a narrow particle size distribution and excellent abrasion resistance.
Description
관련 출원(들)과의 상호 인용Cross-reference with related application(s)
본 출원은 2019년 9월 30일자 한국 특허 출원 제10-2019-0121172호, 2019년 10월 25일자 한국 특허 출원 제10-2019-0134089호 및 2020년 9월 24일자 한국 특허 출원 제10-2020-0123874호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application is for Korean Patent Application No. 10-2019-0121172 filed on September 30, 2019, Korean Patent Application No. 10-2019-0134089 filed on October 25, 2019, and Korean Patent Application No. 10-2020 filed on September 24, 2020. It claims the benefit of the priority based on No. -0123874, and all contents disclosed in the literature of the Korean patent application are included as part of this specification.
본 발명은 프로필렌의 암모산화용 촉매, 이의 제조 방법, 이를 이용한 프로필렌의 암모산화 방법에 관한 것이다.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.
프로필렌의 암모산화 공정은, 암모니아와 프로필렌을 반응시키는 환원 반응과 산소에 의해 재산화되는 매커니즘을 기반으로 하며, 그 반응물(즉, 프로필렌)의 전환율, 반응 생성물(즉, 아크릴로니트릴)의 선택도 및 수율을 높이기 위한 다양한 조성의 촉매가 연구되어 왔다.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.
구체적으로, Mo(몰리브덴)-Bi(비스무스) 산화물 촉매가 제시된 이래, 그 촉매 활성과 안정성을 높이기 위해 다양한 산화 상태를 가지는 금속이 첨가된 촉매들이 연구된 바 있다. 그 결과, 첨가된 금속 종류나 양에 따라, 아크릴로니트릴의 수율은 초기 연구 대비 향상된 편이다.Specifically, since the Mo (molybdenum)-Bi (bismuth) oxide catalyst was presented, catalysts to which metals having various oxidation states were added have been studied in order to increase the catalytic activity and stability. As a result, depending on the type or amount of metal added, the yield of acrylonitrile is improved compared to the initial study.
다만, 촉매 조성의 다양화에도 불구하고, 그 구조 및 물성에 대한 연구가 부족하여, 프로필렌의 암모산화 시 반응물(즉, 프로필렌)의 전환율과 반응 생성물(즉, 아크릴로니트릴)의 선택도를 현저하게 높이는 데에는 한계가 있었다.However, despite the diversification of the catalyst composition, studies on its structure and physical properties were insufficient, and thus the conversion rate of the reactant (i.e., propylene) and the selectivity of the reaction product (i.e., acrylonitrile) were remarkable during the ammoxidation of propylene. There was a limit to the height of it.
구체적으로, 목적하는 조성의 금속 전구체와 나노 실리카 졸을 공침시킨 뒤, 분무 건조하고 소성함으로써, 금속 산화물 입자와 실리카 입자가 집합된 2차 입자 구조의 촉매를 얻는 것이 일반적이다.Specifically, it is common to obtain a catalyst having a secondary particle structure in which metal oxide particles and silica particles are aggregated by co-precipitation of a metal precursor having a desired composition and a nano silica sol, followed by spray drying and firing.
이에 따르면 입도 분포가 넓은 2차 입자가 수득되므로, 후처리로써 분급 공정을 필요로 한다. 더욱이, 상기 2차 입자 구조의 촉매는 마찰에 취약하여, 유동층 반응기 내에서 진행되는 프로필렌의 암모산화 반응 중 미모되거나 손상될 수 있고, 지속적으로 촉매를 추가 공급해주어야 하는 단점이 있다.According to this, secondary particles having a wide particle size distribution are obtained, and thus a classification process is required as a post-treatment. Moreover, 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.
본 발명은, 외부 표면부(즉, 촉매의 표면)뿐만 아니라 그 내부 표면(기공) 또한 반응에 참여할 수 있면서도, 입도 분포가 균일한 프로필렌의 암모산화용 촉매를 제공하고, 이러한 촉매를 사용함으로써 더 높은 수율로 아크릴로니트릴을 제조하기 위한 것이다.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.
구체적으로, 본 발명의 일 구현예에서는, 특정 조성의 금속 산화물이 실리카 담체에 담지된 구조를 가지고, 이처럼 담지된 상태에서의 입도 분포가 균일한 프로필렌의 암모산화용 촉매를 제공한다.Specifically, in one embodiment of the present invention, 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.
상기 일 구현예의 촉매는, 반응에 참여할 수 있는 유효 표면적이 넓어 촉매 효율과 반응성이 높으면서도, 분급 공정 없이도 미분 함량이 적고 균일한 입도 분포를 나타낼 수 있다.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.
따라서, 상기 일 구현예의 촉매를 사용하면, 더 높은 비율로 프로필렌을 전환시키면서, 더 높은 선택도 및 수율로 아크릴로니트릴을 제조할 수 있다.Therefore, by using the catalyst of one embodiment, it is possible to prepare acrylonitrile with higher selectivity and yield while converting propylene at a higher ratio.
도 1은, 공침과 분무건조를 이용하여 제조된 촉매를 모식적으로 도시한 것이다.1 schematically shows a catalyst prepared using coprecipitation and spray drying.
도 2은, 상기 일 구현예에 따른 촉매를 모식적으로 도시한 것이다.2 schematically shows a catalyst according to the embodiment.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시 예를 가질 수 있는 바, 특정 실시 예들을 예시하고 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.In the present invention, various transformations can be applied and various embodiments may be provided, and specific embodiments will be illustrated and described in detail. However, this is not intended to limit the present invention to a specific embodiment, it should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted.
또한, 이하에서 사용될 제 1, 제 2 등과 같이 서수를 포함하는 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 상기 구성요소들은 상기 용어들에 의해 한정되지는 않는다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다. 예를 들어, 본 발명의 권리 범위를 벗어나지 않으면서 제 1 구성요소는 제2 구성요소로 명명될 수 있고, 유사하게 제 2 구성요소도 제 1 구성요소로 명명될 수 있다.In addition, terms including ordinal numbers such as 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.
단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof does not preclude in advance.
이하에서 "입경 Dv"은, 입경에 따른 부피 누적 분포의 v% 지점에서의 입경을 의미한다. 즉, D50은 입경에 따른 부피 누적 분포의 50% 지점에서의 입경이며, D90은 입경에 따른 부피 누적 분포의 90% 지점에서의 입경을, D10은 입경에 따른 부피 누적 분포의 10% 지점에서의 입경이다.Hereinafter, "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.
이하, 도면을 참조하여 상기 일 구현예의 프로필렌의 암모산화용 촉매를 상세히 설명하도록 한다.Hereinafter, a catalyst for ammoxidation of propylene according to the embodiment will be described in detail with reference to the drawings.
프로필렌의 암모산화용 촉매Catalyst for ammoxidation of propylene
본 발명의 일 구현예에서는, 하기 화학식 1로 표시되는 금속 산화물이 실리카 담체에 담지되고; 상기 금속 산화물이 실리카 담체에 담지된 상태에서, D50 입경이 30 내지 300 ㎛이고, D10 입경, D50 입경 및 D90 입경이 하기 식 1의 관계를 만족하는 것인, 프로필렌의 암모산화용 촉매를 제공한다:In one embodiment of the present invention, 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 μm, 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. :
[식 1][Equation 1]
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
A 는 Ni, Mn, Co, Zn, Mg, Ca, 및 Ba 중 하나 이상의 원소이고,A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,
B는 Li, Na, K, Rb, 및 Cs 중 하나 이상의 원소이고,B is one or more elements of Li, Na, K, Rb, and Cs,
C는 Cr, W, B, Al, Ca, 및 V 중 하나 이상의 원소이고,C is one or more elements of Cr, W, B, Al, Ca, and V, and
상기 a 내지 e, 및 x는 각각 원자 또는 원자단의 분율이며, a는 0.1 내지 5이고, b는 0.1 내지 5 이고, c는 0.01 내지 10이고, d는 0.01 내지 2이며, e는 0 내지 10이고, x는 24 내지 48이다.Wherein 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.
일반적으로 알려진 프로필렌의 암모산화용 촉매는, 공침과 분무건조를 통해 제조되어, 금속 산화물 나노입자와 실리카 나노입자가 집합된 2차 입자 구조로 제공된다(도 1).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).
이는, 내부 및 외부에 금속 산화물 입자가 골고루 분포된 대신, 프로필렌의 암모산화 반응에 참여할 수 있는 부위가 외부 표면부(즉, 2차 입자의 표면)로 제한되고, 작은 표면적을 제공하므로, 프로필렌의 암모산화 반응 중 촉매 표면으로부터 탈착되는 암모니아의 양이 많다.This is because, instead of evenly distributed inside and outside of the metal oxide particles, a portion that can participate in the ammoxidation reaction of propylene is limited to the outer surface portion (i.e., the surface of the secondary particles), and provides a small surface area. The amount of ammonia desorbed from the catalyst surface during ammoxidation reaction is large.
그에 반면, 상기 일 구현예의 촉매는, 함침법으로 제조되어, 금속 산화물이 실리카 담체에 담지된 구조로 제공될 수 있다(도 2).On the other hand, 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).
예를 들어, 목적하는 금속 산화물의 화학양론적 몰비를 만족하도록 제조된 금속 전구체 용액에 실리카 담체를 담가, 상기 실리카 담체 내에 상기 금속 전구체 용액을 함침시킬 수 있다.For example, 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.
이후, 건조 공정을 통해 용매(즉, 물)를 제거하면, 실리카 담체의 기공벽에 금속 전구체가 잔존하게 되고, 소성 공정에서 금속 전구체가 산화되면서 실리카 담체 기공벽을 연속적으로 코팅하는 막을 형성할 수 있다.Thereafter, when the solvent (i.e., water) is removed through the drying process, 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. have.
이처럼 제조된 일 구현예의 촉매는, 제조 후 후처리로써 분급 공정을 진행하지 않더라도, 공침과 분무건조를 통해 동일한 조성으로 제조된 촉매보다 미분 함량이 적고 내구성은 뛰어날 수 있다.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.
또한, 상기 일 구현예의 촉매는, 암모산화 반응의 활성을 높이는 것으로 알려진 Mo 및 Bi뿐만 아니라, 프로필렌의 암모산화 반응에 대한 적합한 수준의 활성점을 형성하는 금속을 더 포함하도록 금속 산화물 조성을 제어함으로써 촉매 활성을 더욱 높일 수 있다.In addition, 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.
특히, 상기 일 구현예의 촉매에서, 실리카 담체의 내부 기공에 상기 금속 산화물을 골고루 담지하여 프로필렌의 암모산화 반응에 참여할 수 있는 부위가 외부 표면부(즉, 촉매의 표면)뿐만 아니라 그 내부 표면(기공)으로 확장되는 이점이 있다.Particularly, in the catalyst of one embodiment, 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.
나아가, 상기 일 구현예의 촉매는, 함침법을 이용하여 금속 산화물이 실리카 담체에 담지된 구조로 구현될 수 있고, 분급 공정 없이도 미분 함량이 적고, 균일한 입도 분포를 나타낼 수 있다.Further, 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.
더욱이, 상기 금속 산화물이 실리카 담체에 담지된 구조 및 균일한 입도 분포 상 우수한 내마모성을 발현하여, 유동층 반응기 내에서 진행되는 프로필렌의 암모산화 반응 중 촉매의 추가 공급 없이도, 더 높은 수율로 아크릴로니트릴을 제조할 수 있다.Moreover, 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.
이하, 상기 일 구현예의 촉매를 보다 상세히 설명한다,Hereinafter, the catalyst of the embodiment will be described in more detail,
촉매의 구조Catalyst structure
상기 일 구현예의 촉매는, 제2 기공을 포함하는 실리카 담체; 상기 제2 기공의 벽면을 연속적으로 코팅하고, 상기 화학식 1로 표시되는 금속 산화물을 포함하는 내부 코팅층; 및 상기 제2 기공 내부에 위치하고, 상기 내부 코팅층을 제외한 빈 공간을 차지하는 제1 기공;을 포함하는 구조일 수 있다.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.
구체적으로, 상기 일 구현예의 촉매는, 에그-쉘(egg-shell) 구조를 가질 수 있다.Specifically, the catalyst of the embodiment may have an egg-shell structure.
이를 위해, 상기 실리카 담체로는, 비다공성(非多孔性) 코어부; 및 상기 비다공성(非多孔性) 코어의 표면에 위치하고, 제2 기공을 포함하는, 다공성(多孔性) 쉘부;을 포함하는 것을 사용할 수 있다.To this end, 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.
보다 구체적으로, 상기 다공성(多孔性) 쉘은 표면의 요부(凹部) 및 철부(凸部)를 포함하고, 상기 요부(凹部)는 상기 제2 기공이 상기 다공성(多孔性) 쉘의 표면으로 열려서 형성된 것일 수 있다.More specifically, 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.
이에 따라, 상기 일 구현예의 촉매는, 상기 다공성(多孔性) 쉘의 요부 및 철부를 연속적으로 코팅하고, 상기 화학식 1로 표시되는 금속 산화물을 포함하는 코팅층; 및 상기 실리카 담체의 요부에, 상기 코팅층을 제외한 빈 공간을 차지하는 제1 기공;을 포함하는 구조를 가질 수 있다.Accordingly, 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.
촉매의 D50 입경 및 입도 분포의 균일성Uniformity of D50 particle size and particle size distribution of catalyst
상기 일 구현예의 촉매는, 금속 산화물이 실리카 담체에 담지된 상태에서, D50 대비 입도 분포가 균일하고, 미분 함량이 적을 수 있다.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.
구체적으로, 상기 일 구현예의 촉매는, D50 입경이 30 내지 200 ㎛일 수 있고, 이러한 D50 입경에 대한 [D90 입경과 D10 입경의 차이]의 비가 2.0 미만으로, 좁은 입도 분포를 나타낼 수 있다.Specifically, the catalyst of the embodiment may have a D50 particle diameter of 30 to 200 µm, 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.
보다 구체적으로, 상기 일 구현예의 촉매는, D50 입경의 하한을 30 ㎛ 이상, 35 ㎛ 이상, 40 ㎛ 이상, 또는 45 ㎛ 이상으로 하면서, 상한을 300 ㎛ 이하, 280 ㎛ 이하, 260 ㎛ 이하, 240 ㎛ 이하, 220 ㎛ 이하, 또는 200 ㎛ 이하로 할 수 있다.More specifically, the catalyst of one embodiment has a lower limit of D50 particle size of 30 µm or more, 35 µm or more, 40 µm or more, or 45 µm or more, and an upper limit of 300 µm or less, 280 µm or less, 260 µm or less, 240 It can be made into µm or less, 220 µm or less, or 200 µm or less.
또한, 상기 일 구현예의 촉매는, D50 입경에 대한 [D90 입경과 D10 입경의 차이]의 비를 2.0 미만, 1.9 이하, 1.8 이하, 1.7 이하, 1.6 이하, 또는 1.5 이하로 하여, 좁은 입도 분포를 나타낼 수 있다.In addition, 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.
다시 말해, 상기 일 구현예의 촉매가 나타내는 입도 분포의 균일성은, 그 D50 입경 대비 D10 입경 및 D90 입경이 하기 식 1, 구체적으로 하기 식 1-1의 관계를 만족하는 점으로부터 뒷받침될 수 있다:In other words, 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:
[식 1][Equation 1]
[식 1-1][Equation 1-1]
촉매의 마모 손실량Catalyst wear loss
입자의 마모란 고체인 입자가 기계적, 화학적 과정을 통하여 분해되는 현상을 말한다. 입자 마모는 마멸(abrasion) 와 파쇄(fragmentation)의 두 가지 형태로 분류되며, 두 가지 형태가 함께 일어날 수도 있다Particle 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.
특히, 유동층 공정에서 촉매 입자가 마모되어 미분화될 수 있고, 지속적으로 마모된 양만큼 촉매를 보충(make-up)할 필요가 있고, 이는 전체 공정의 경제성에 영향을 줄 수 있다.Particularly, in the fluidized bed process, 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.
입자의 마모를 측정하는 기준으로는 ASTM9797-00 법이 알려져 있다. 이는, 내경 35 mm이고 높이 710 mm인 수직형 내관에 50 g의 촉매(W0)를 충진한 후, 10L/min으로 N
2 가스를 흘린 다음, 5시간 후 미분 필터에 포집된 촉매의 양(W)을 측정하여, 아래의 식을 이용하여 내마모성(마모 손실, Attrition loss)을 측정하는 방법에 해당된다.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.
내마모성(마모 손실, attrition loss) (%) = (W0)/W X 100Abrasion resistance (attrition loss) (%) = (W0)/W X 100
상기 일 구현예의 촉매는, 상기 ASTM9797-00 법에 따라 측정된 내마모성(마모 손실, Attrition loss)이 9 % 이하, 8.7 % 이하, 8.4 % 이하, 8.2 % 이하, 또는 8 % 이하로, 그 손실량이 매우 적고, 내마모성이 우수할 수 있다.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.
따라서, 공침과 분무 건조를 통해 제조된 2차 입자 구조의 촉매 대비, 상기 일 구현예의 촉매는 우수한 내마모성을 나타내며, 유동층 반응기 내에서 진행되는 프로필렌의 암모산화 반응 중 촉매의 추가 공급 없이도, 더 높은 수율로 아크릴로니트릴을 제조할 수 있다.Therefore, compared to the catalyst of the secondary particle structure prepared through coprecipitation and spray drying, 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.
금속 산화물의 조성Composition of metal oxides
한편, 상기 일 구현예의 촉매와 동일한 구조를 가지더라도, 상기 금속 산화물을 구성하는 성분들의 종류와 함량이 상기 화학식 1을 만족하지 못한다면, 프로필렌의 암모산화에 부족하거나 지나치게 밀도가 높은 촉매의 활성점이 형성될 수 있다.On the other hand, even if it has the same structure as the catalyst of the embodiment, if the type and content of the components constituting the metal oxide do not satisfy the above formula (1), the active sites of the catalyst having insufficient or excessively high density for ammoxidation of propylene are formed. Can be.
이에, 상기 금속 산화물을 구성하는 종류와 함량은 상기 화학식 1을 만족하도록 할 필요가 있다.Accordingly, it is necessary to satisfy the type and content of the metal oxide to satisfy the formula (1).
특히, 상기 금속 산화물이 하기 화학식 1-1로 표시되는 것일 때, Fe의 몰리브덴의 격자 산소의 이동 속도를 높여 전환율을 높이는 효과, Co의 몰리브덴과의 복합 산화물 형성으로 프로필렌의 부분 산화 반응 특성을 높이는 효과, 및 K의 몰리브덴을 포함한 복합 산화물의 활성점을 분산시켜 AN 선택도를 높이는 효과의 시너지 효과로, 프로필렌의 암모산화 반응에서의 활성도가 더 높아질 수 있다:In particular, when 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:
[화학식 1-1][Formula 1-1]
상기 화학식 1-1에서, 상기 a 내지 d, 및 x는 각각 원자 또는 원자단의 분율이며, a는 0.1 내지 5이고, 구체적으로 0.1 내지 2.0 이고, b는 0.1 내지 5 이고, 구체적으로 0.5 내지 3.0이고, c는 0.01 내지 10이고, 구체적으로 1 내지 10이고, d는 0.01 내지 2이며, 구체적으로 0.01 내지 1.0 이며, x는 24 내지 48, 구체적으로 28 내지 45일수 있다.In Formula 1-1, 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.
금속 산화물:실리카 담체의 중량비Metal oxide: weight ratio of silica carrier
상기 일 구현예의 촉매는, 상기 금속 산화물 및 상기 실리카 담체를 10:90 내지 15:95, 구체적으로 20:80 내지 50:50, 예컨대 15:85 내지 35:65의 중량비(금속 산화물:실리카 담체)로 포함할 수 있다.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.
이 범위 내에서, 상기 일 구현예의 촉매는 높은 활성도와 함께 높은 아크릴로 니트릴의 선택도를 가질 수 있다.Within this range, the catalyst of the embodiment may have high selectivity of acrylonitrile with high activity.
프로필렌의 암모산화용 촉매의 제조 방법Method for producing a catalyst for ammoxidation of propylene
본 발명의 다른 일 구현예에서는, 함침법을 이용하여 전술한 일 구현예의 촉매를 제조하는 방법을 제공한다.In another embodiment of the present invention, a method of preparing the catalyst of the above-described embodiment is provided using an impregnation method.
앞서 간단히 설명한 바와 같이, 상기 일 구현예의 촉매는, 함침법을 이용하여 상기 실리카 담체에 금속 전구체 용액을 담지시키고, 건조 후 소성시키는 일련의 공정을 통해 제조될 수 있다.As briefly described above, 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.
보다 구체적으로, 상기 일 구현예의 촉매를 제조하는 방법으로,More specifically, as a method of preparing the catalyst of the embodiment,
구연산, 옥살산, 또는 이들의 혼합물인 첨가제; 및 Mo 전구체를 포함하는 제1 전구체 용액을 제조하는 단계,Additives that are citric acid, oxalic acid, or mixtures thereof; And preparing a first precursor solution including a Mo precursor,
Bi 전구체, Fe 전구체, A 전구체(A= Ni, Mn, Co, Zn, Mg, Ca, 및 Ba 중 하나 이상의 원소), 및 B 전구체(B= Li, Na, K, Rb, 및 Cs 중 하나 이상의 원소)를 포함하는 제2 전구체 용액을 제조하는 단계,Bi precursor, Fe precursor, A precursor (A = one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba), and B precursor (B = one or more of Li, Na, K, Rb, and Cs Element) preparing a second precursor solution,
금속의 몰비가 하기 화학식 1의 화학양론적 몰비를 만족하도록 하며, 상기 제1 및 제2 전구체 용액을 혼합하는 단계,Mixing the first and second precursor solutions so that the molar ratio of the metal satisfies the stoichiometric molar ratio of Formula 1 below,
상기 제1 및 제2 전구체 용액의 혼합물을 실리카 담체에 담지시키는 단계,Supporting the mixture of the first and second precursor solutions on a silica carrier,
상기 제1 및 제2 전구체 용액의 혼합물이 담지된 실리카 담체를 건조시키는 단계, 그리고Drying the silica carrier on which the mixture of the first and second precursor solutions is supported, and
상기 건조된 물질을 소성하는 단계를 포함하는 방법을 제공한다:There is provided a method comprising the step of firing the dried material:
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
A 는 Ni, Mn, Co, Zn, Mg, Ca, 및 Ba 중 하나 이상의 원소이고,A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,
B는 Li, Na, K, Rb, 및 Cs 중 하나 이상의 원소이고,B is one or more elements of Li, Na, K, Rb, and Cs,
C는 Cr, W, B, Al, Ca, 및 V 중 하나 이상의 원소이고,C is one or more elements of Cr, W, B, Al, Ca, and V, and
상기 a 내지 e, 및 x는 원자 또는 원자단의 분율이며, a는 0.1 내지 5이고, b는 0.1 내지 5 이고, c는 0.01 내지 10이고, d는 0.01 내지 2이며, e는 0 내지 10이고, x는 24 내지 48이다.Wherein 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.
제1 전구체 용액의 제조 공정Manufacturing process of the first precursor solution
상기 제1 전구체 용액을 제조하는 단계는, 20 내지 80 ℃의 물, Mo 전구체 및 첨가제를 용해시켜, 물, Mo 전구체 및 첨가제를 포함하는 수용액을 제조하는 단계일 수 있다.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.
상기 제1 전구체 용액을 제조하는 단계에서는, 구연산, 옥살산, 또는 이들의 혼합물을 포함하는 첨가제가 사용된다.In the step of preparing the first precursor solution, an additive including citric acid, oxalic acid, or a mixture thereof is used.
상기 첨가제는 공침과 분무건조를 이용하는 촉매 제조 공정에서는 강도 조절제로 기능하지만, 이는 일 구현예에서 상기 제1 전구체 용액을 투명하게 하는 기능을 한다.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.
상기 첨가제의 첨가 시, 상기 몰리브덴 전구체 및 상기 첨가제의 중량비는, 1 :0.1 내지 1:1, 구체적으로 1:0.2 내지 1:0.7를 만족하도록 할 수 있고, 이 범위 내에서 몰리브덴 전구체의 용해도가 증가할 수 있으나 이에 제한되는 것은 아니다.When the additive is added, 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.
제2 전구체 용액의 제조 공정Manufacturing process of the second precursor solution
상기 제1 전구체 용액에 포함된 Mo 전구체를 제외하고, 나머지 금속 전구체를 포함하는 제2 전구체 용액을 제조할 수 있다.Excluding the Mo precursor included in the first precursor solution, a second precursor solution including the remaining metal precursors may be prepared.
구체적으로, 상기 제2 전구체 용액을 제조하는 단계는, 20 내지 50 ℃의 물에, Bi 전구체, Fe 전구체, A 전구체, 및 B 전구체를 필수적으로 포함하며, 선택적으로 C 전구체(Cr, W, B, Al, Ca, 및 V 중 하나 이상의 원소)를 더 포함하는 제2 전구체 용액을 제조하는 것일 수 있다.Specifically, 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).
보다 구체적으로, 상기 제2 전구체 용액을 제조하는 단계에서, 최종적으로 목적하는 촉매 내 금속 산화물 조성을 고려하여, Mo 전구체를 제외한 금속 전구체의 종류를 선택할 수 있다.More specifically, in the step of preparing the second precursor solution, 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.
예컨대, 전술한 화학식 1-1을 만족하는 금속 산화물 조성을 고려하여, 물, Bi 전구체, Fe 전구체, Co 전구체, 및 K 전구체를 포함하는 제2 전구체 용액을 제조할 수 있다.For example, in consideration of the metal oxide composition satisfying Formula 1-1, a second precursor solution including water, a Bi precursor, an Fe precursor, a Co precursor, and a K precursor may be prepared.
상기 제1 및 제2 전구체 용액을 제조하는 공정은 각각 독립적이고, 제조 순서가 제한되는 것은 아니다.Processes of preparing the first and second precursor solutions are each independent, and the order of preparation is not limited.
상기 제1 및 제2 전구체 용액 혼합물의 담체 내 담지 공정Supporting process of the first and second precursor solution mixture in a carrier
상기 제1 및 제2 전구체 용액을 혼합한 후, 이를 실리카 담체에 담지시킬 수 있다.After mixing the first and second precursor solutions, they may be supported on a silica carrier.
여기서, 앞서 언급한 제2 기공을 포함하는 실리카 담체를 상기 제1 및 제2 전구체 용액의 혼합물에 투입하여, 상기 실리카 담체 내 제1 기공에 상기 제1 및 제2 전구체 용액의 혼합물이 담지되도록 할 수 있다.Here, 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.
구체적으로, 상기 금속 산화물이 담지되지 않은 실리카 담체 그 자체의 D50 크기가 20 내지 400 ㎛일 수 있다.Specifically, the D50 size of the silica carrier on which the metal oxide is not supported may be 20 to 400 μm.
보다 구체적으로, 상기 금속 산화물이 담지되지 않은 실리카 담체는, 그 자체의 D50 크기가 20 내지 400 ㎛이면서; 직경이 10 내지 200 ㎚인 제2 기공을 포함할 수 있다.More specifically, the silica carrier on which the metal oxide is not supported has a D50 size of 20 to 400 μm; It may include second pores having a diameter of 10 to 200 nm.
보다 구체적으로, 상기 금속 산화물이 담지되지 않은 실리카 담체 그 자체의 D50은, 하한을 20 ㎛ 이상, 25㎛ 이상, 30 ㎛ 이상, 35 ㎛ 이상, 40 ㎛ 이상, 또는 43 ㎛ 이상으로 하고, 상한을 400 ㎛ 이하, 350 ㎛ 이하, 300 ㎛ 이하, 270 ㎛ 이하, 230 ㎛ 이하, 또는 200 ㎛ 이하로 할 수 있다.More specifically, the D50 of the silica carrier itself without metal oxide has a lower limit of 20 µm or more, 25 µm or more, 30 µm or more, 35 µm or more, 40 µm or more, or 43 µm or more, and the upper limit is It may be 400 µm or less, 350 µm or less, 300 µm or less, 270 µm or less, 230 µm or less, or 200 µm or less.
또한, 상기 금속 산화물이 담지되지 않은 실리카 담체 그 자체에 포함된 제 2 기공은, 직경이 10 ㎚ 이상, 15 ㎚ 이상, 또는 20 ㎚ 이상이고, 200 ㎚이하, 100 ㎚ 이하, 50 ㎚ 이하, 40 ㎚ 이하, 또는 30 ㎚ 이하로 할 수 있다.In addition, 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.
상기 제1 및 제2 전구체 용액 혼합물이 담체된 담체의 건조 공정Drying process of the carrier carrying the first and second precursor solution mixtures
상기 제1 및 제2 전구체 용액의 혼합물이 담지된 실리카 담체를 건조시키는 단계는, 상기 제1 및 제2 전구체 용액의 혼합물이 담지된 실리카 담체를 120 내지 160 mbar에서 1차 진공 건조하는 단계, 및 상기 1차 진공 건조된 물질을 30 내지 50 mbar에서 2차 진공 건조하여, 상기 제1 및 제2 전구체 용액의 혼합물이 담지된 실리카 담체를 수득하는 단계를 포함할 수 있다.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.
구체적으로, 상기 1차 진공 건조는 60 내지 80 ℃에서 1 내지 2 시간 동안 수행하고, 상기 2차 진공 건조는 80 내지 100 ℃에서 15 내지 45 분 동안 수행함으로써, 용매(즉, 물)이 제거되고, 상기 제1 및 제2 전구체만 제1 기공의 벽면에 잔존할 수 있다.Specifically, 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. , Only the first and second precursors may remain on the walls of the first pores.
상기 2차 진공 건조가 완료된 물질을 바로 소성할 수 있지만, 상압에서 3차 건조함으로써, 상기 2차 진공 건조 후 남아있는 용매(즉, 물)까지도 효과적으로 제거할 수 있다.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.
구체적으로, 상기 3차 건조는 100 내지 120 ℃에서 20 내지 30 시간 동안 수행될 수 있다.Specifically, the third drying may be performed at 100 to 120 °C for 20 to 30 hours.
다만, 이는 예시일 뿐이며, 용매(즉, 물)는 제거되고, 상기 제1 및 제2 전구체가 담지된 담체를 수득할 수 있는 건조 조건이라면 특별히 한정되지 않는다.However, this is only an example, and the solvent (ie, water) is removed, and 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.
최종 소성 공정Final firing process
최종적으로, 상기 건조된 물질, 즉, 상기 제1 및 제2 전구체가 담지된 담체를 500 내지 700 ℃의 온도 범위 내에서 2 내지 5 시간 동안 소성시켜, 최종적으로 촉매를 수득할 수 있다.Finally, 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.
다만, 상기 건조 및 소성의 각 조건은 예시일 뿐이며, 상기 담체의 내부 기공으로부터 용매를 충분히 제거하고, 금속 전구체를 산화시킬 수 있는 조건이라면 충분하다.However, the 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.
프로필렌의 암모산화 방법Propylene ammoxidation method
본 발명의 또 다른 일 구현예에서는, 반응기 내에서, 전술한 일 구현예의 촉매 존재 하에 프로필렌 및 암모니아를 반응시키는 단계를 포함하는, 프로필렌의 암모산화 방법을 제공한다.In another embodiment of the present invention, there is provided 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.
상기 일 구현예의 촉매는, 높은 활성도와 함께 고온 안정성을 가지며, 프로필렌의 암모산화 반응에 이용되어 프로필렌의 전환율, 아크릴로니트릴의 선택도 및 수율을 높일 수 있다.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.
상기 일 구현예의 촉매 이외의 사항들에 대해서는, 당업계에 일반적으로 알려진 사항을 참고할 수 있어, 더 이상의 상세한 설명을 생략한다.For matters other than the catalyst of the embodiment, it is possible to refer to matters generally known in the art, and a detailed description thereof will be omitted.
이하, 본 발명의 구현예를 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 발명의 구현예를 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다.Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the invention, and the contents of the present invention are not limited by the following examples.
실시예 1Example 1
(1) 전구체 용액의 제조 공정(1) Manufacturing process of precursor solution
60 ℃의 증류수에 10.592 g의 Mo 전구체((NH
4)
6·Mo
7O
24) 및 0.1 g의 구연산(Citric acid)을 투입하고 혼합하여, Mo 전구체 용액을 제조하였다.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.
이와 독립적으로, 상온의 증류수에 1.819g 의 Bi 전구체(Fe(NO
3)
35H
2O), 9.488 g의 Co 전구체(Co(NO
3)
2·6H
2O), 2.990 g의 Fe 전구체(Fe(NO
3)
2·9H
2O), 및 0.354 g의 K 전구체(KNO
3)를 투입하고, 1.46 g의 질산(HNO
3)을 첨가한 뒤 혼합하여, Bi, Fe, Co, 및 K 전구체 혼합 용액을 제조하였다.Independently, in distilled water at room temperature , 1.819 g of Bi precursor (Fe(NO 3 ) 3 5H 2 O), 9.488 g of Co precursor (Co(NO 3 ) 2 ·6H 2 O), 2.990 g of Fe precursor (Fe (NO 3 ) 2 ·9H 2 O), and 0.354 g of K precursor (KNO 3 ) were added, and 1.46 g of nitric acid (HNO 3 ) was added and then mixed, and Bi, Fe, Co, and K precursors were mixed. The solution was prepared.
상기 Mo 전구체 용액; 및 상기 Bi, Fe, Co, 및 K 전구체 혼합 용액을 혼합하여, Mo, Bi, Fe, Co, 및 K의 전구체 혼합 용액을 완성하였다.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.
상기 전구체 혼합 용액에서, 증류수의 총량은 36.59 g이다.In the precursor mixture solution, the total amount of distilled water is 36.59 g.
(2) 실리카 담체 내 전구체 용액의 담지 공정 (함침법 이용)(2) Supporting process of precursor solution in silica carrier (using impregnation method)
D50 입경이 55 ㎛이고, 내부 기공 크기가 24.4 nm 인 실리카(SiO
2, D60-60A, AGC-Si) 입자를 담체로 사용하였다. Silica (SiO 2 , D60-60A, AGC-Si) particles having a D50 particle diameter of 55 μm and an internal pore size of 24.4 nm were used as a carrier.
상기 Mo, Bi, Fe, Co, 및 K의 전구체 혼합 용액에 상기 실리카 담체를 투입하고, 상온 및 80 ℃에서 순차적으로 각각 2시간 동안 교반하여, 상기 실리카 담체의 내부 기공에 상기 Mo, Bi, Fe, Ni, Co, 및 K 전구체 혼합 용액이 충분히 담지되도록 하였다.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.
(3) 전구체 용액이 담치된 실리카 담체의 건조 및 소성 공정(3) Drying and sintering process of the silica carrier loaded with the precursor solution
이후, 상기 Bi, Fe, Co, 및 K의 전구체 혼합 용액이 담지된 실리카 담체를 회수하여 회전 진공 건조기에 투입한 뒤, 140 mbar의 압력 및 70 ℃의 온도 조건으로 1시간 40분간 1차 진공 건조하고, 연이어 40 mbar의 압력 및 90 ℃의 온도 조건으로 30 분간 2차 진공 건조하였다.Thereafter, 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.
상기 2차 진공 건조까지 완료된 물질을 회수하여 오븐(oven)에 투입하고, 상압 및 110 ℃ 온도 조건으로 24 시간 동안 3차 건조시킨 뒤, 공기 분위기의 Box 소성로에서 580 ℃의 온도를 유지하면서 3 시간 동안 열처리하여, 최종적으로 실시예 1의 촉매를 수득하였다.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 ℃ temperature conditions, while maintaining the temperature of 580 ℃ in the box sintering furnace in an air atmosphere 3 hours During heat treatment, the catalyst of Example 1 was finally obtained.
(4) 플로필렌의 암모산화 공정(4) Process of ammoxidation of flophyllene
내경이 3/8 인치(inch)인 관형 반응기 내, 촉매의 활성화를 위하여 석영 섬유(Quartz wool) 0.05 g가 충진하고, 실시예 1의 촉매 0.2 g을 반응기 내에 충진시켰다.In a tubular reactor having an inner diameter of 3/8 inch (inch), 0.05 g of quartz wool was charged for activation of the catalyst, and 0.2 g of the catalyst of Example 1 was charged into the reactor.
이처럼 석영 섬유와 촉매가 충진된 반응기의 내부 압력은 상압 (1atm)으로 유지시키고, 10 ℃/min의 승온 속도로 반응기 내부 온도를 승온시키면서, 전처리 공정으로써 질소와 암모니아 가스를 흘려주었다. 이에 따라 반응기 내부 온도가 암모산화 반응이 가능한 온도인 400 ℃에 도달한 뒤, 15분 동안 환원 기체의 분위기 하에서 유지시키며 충분한 전처리가 이루어지도록 하였다.As described above, 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.
이처럼 전처리가 완료된 반응기에, 반응물인 프로필렌 및 암모니아와 함께 공기(air)를 공급하며, 프로필렌의 암모산화 공정을 수행하였다. 이때, 반응물의 공급량은 프로필렌:암모니아:공기=0.8:1.2:8 부피비가 되도록 구성하면서, 프로필렌, 암모니아, 및 공기의 총 중량공간속도(WHSV: weight hourly space velocity)는 1.54 h
-1이 되도록 하였다. In the reactor where the pretreatment was completed, air was supplied together with propylene and ammonia as reactants, and the ammoxidation process of propylene was performed. At this time, the supply amount of the reactants was configured to be a propylene:ammonia:air = 0.8:1.2:8 volume ratio, while the total weight hourly space velocity (WHSV) of propylene, ammonia, and air was 1.54 h -1. .
상기 암모산화 반응 종료 후 그 생성물을 회수하고, 아크릴로니트릴이 잘 생성되었는지 확인하기 위해 다양한 장비를 사용하여 분석하였다.After completion of the ammoxidation reaction, the product was recovered and analyzed using various equipment to confirm whether acrylonitrile was well produced.
그 분석 방법, 분석 결과 등에 대해서는, 후술되는 실험예에서 상세히 기술한다.The analysis method, analysis result, etc. will be described in detail in the experimental examples described later.
실시예 2 내지 7Examples 2 to 7
(1) 촉매의 제조 공정 (함침법 이용)(1) catalyst manufacturing process (using the impregnation method)
하기 표 1에 기재된 조성에 따라 전구체 용액을 제조하고, 하기 표 2에 기재된 실리카 담체를 사용하되, 나머지는 실시예 1과 동일하게 하여 실시예 2 내지 7의 각 촉매를 제조하였다.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.
(2) 플로필렌의 암모산화 공정(2) Process of ammoxidation of flophyllene
또한, 실시예 1의 촉매 대신 실시예 2 내지 7의 각 촉매를 사용하여 플로필렌의 암모산화 공정을 수행한 뒤 그 생성물을 회수하고, 실시예 1과 마찬가지로 분석을 실시하였다.In addition, instead of the catalyst of Example 1, 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.
비교예 1Comparative Example 1
(1) 촉매의 제조 공정 (공침 후 분무건조 이용)(1) Catalyst manufacturing process (using spray drying after coprecipitation)
우선, 60 ℃의 증류수에 10.592 g의 Mo 전구체((NH
4)
6Mo
7O
24) 및 3.18 g의 구연산(Citric acid)을 투입하고 혼합하여, Mo 전구체 용액을 제조하였다.First, 10.592 g of 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.
이와 독립적으로, 상온의 증류수에 1.819 g의 Bi 전구체(Fe(NO
3)
3·5H
2O), 9.488 g의 Co 전구체(Co(NO
3)
2·6H
2O), 2.900 g의 Fe 전구체(Fe(NO
3)
2·9H
2O), 및 0.354 g의 K 전구체(KNO
3)를 투입하고, 0.83 g의 질산(HNO
3)을 첨가한 뒤 혼합하여, Bi, Fe, Co, 및 K 전구체 혼합 용액을 제조하였다.Independently, in distilled water at room temperature, 1.819 g of Bi precursor (Fe(NO 3 ) 3· 5H 2 O), 9.488 g of Co precursor (Co(NO 3 ) 2 ·6H 2 O), 2.900 g of Fe precursor ( Fe(NO 3 ) 2 ·9H 2 O), and 0.354 g of K precursor (KNO 3 ) were added, and 0.83 g of nitric acid (HNO 3 ) was added and then mixed, and Bi, Fe, Co, and K precursors A mixed solution was prepared.
상기 Mo 전구체 용액; 및 상기 Bi, Fe, Co, 및 K 전구체 혼합 용액을 혼합하고, 여기에 실리카졸 실리카졸 22.53 g(LUDOX AS 40, 고형분 함량: 40 %)을 첨가하여 교반한 다음, Disk-type의 분무 건조기를 사용하여 120 ℃(inlet) 및 230 ℃(outlet) 조건으로 분무 건조하였다.The Mo precursor solution; And the Bi, Fe, Co, and K precursor mixed solution was mixed, 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).
이에 따라 얻어진 분말을 580 ℃에서 3시간 동안 소성하여, 비교예 1의 촉매로 최종 수득하였다.The powder thus obtained was fired at 580° C. for 3 hours, and finally obtained as the catalyst of Comparative Example 1.
(3) 플로필렌의 암모산화 공정(3) Ammoxidation process of flophyllene
실시예 1의 촉매 대신 상기 비교예 1의 촉매를 사용하고, 나머지는 실시예 1과 동일하게 하여 플로필렌의 암모산화 공정을 수행하였다.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.
비교예 1의 암모산화 반응 종료 후 그 생성물을 회수하고, 실시예 1과 마찬가지로 분석을 실시하였다.After completion of the ammoxidation reaction of Comparative Example 1, the product was recovered and analyzed in the same manner as in Example 1.
비교예 2 내지 4Comparative Examples 2 to 4
(1) 촉매의 제조 공정 (함침법 이용)(1) catalyst manufacturing process (using the impregnation method)
하기 표 1에 기재된 조성에 따라 전구체 용액을 제조하고, 하기 표 2에 기재된 실리카 담체를 사용하되, 나머지는 실시예 1과 동일하게 하여 비교예 2 내지 4의 촉매를 제조하였다.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.
(2) 플로필렌의 암모산화 공정(2) Process of ammoxidation of flophyllene
또한, 실시예 1의 촉매 대신 비교예 2 내지 4의 각 촉매를 사용하여 플로필렌의 암모산화 공정을 수행한 뒤 그 생성물을 회수하고, 실시예 1과 마찬가지로 분석을 실시하였다.In addition, after performing the ammoxidation process of flophyllene using each catalyst of Comparative Examples 2 to 4 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
비교예 5Comparative Example 5
(1) 촉매의 제조 공정 (함침법 이용)(1) catalyst manufacturing process (using the impregnation method)
우선, 60 ℃의 증류수에 10.592 g의 Mo 전구체((NH
4)
6·Mo
7O
24) 및 0.53 g의 구연산(Citric acid)을 투입하고 혼합하여, Mo 전구체 용액을 제조하였다.First, 10.592 g of 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.
이와 독립적으로, 상온의 증류수에 1.091 g의 Bi 전구체(Fe(NO
3)
3·5H
2O), 4.365 g의 Co 전구체(Co(NO
3)
2·6H
2O), 3.636 g의 Fe 전구체(Fe(NO
3)
2·9H
2O), 2.908 g의 Ni 전구체(Ni(NO
3)
2·6H
2O), 0.045 g의 K 전구체(KNO
3), 1.954 g의 Ce 전구체(Ce(NO
3)
3·6H
2O), 2.564 g의 Mg 전구체(Mg(NO
3)
2·6H
2O), 및 0.037 g의 Rb 전구체(RbNO
3)를 투입하고, 0.74 g의 질산(HNO
3)을 첨가한 뒤 혼합하여, Bi, Co, Fe, Ni, K, Ce, Mg, 및 Rb 전구체 혼합 용액을 제조하였다.Independently, 1.091 g of Bi precursor (Fe(NO 3 ) 3 ·5H 2 O), 4.365 g of Co precursor (Co(NO 3 ) 2 ·6H 2 O), 3.636 g of Fe precursor ( Fe(NO 3 ) 2 ·9H 2 O), 2.908 g of Ni precursor (Ni(NO 3 ) 2 ·6H 2 O), 0.045 g of K precursor (KNO 3 ), 1.954 g of Ce precursor (Ce(NO 3 ) 3 · 6H 2 O), 2.564 g of Mg precursor (Mg(NO 3 ) 2 · 6H 2 O), and 0.037 g of Rb precursor (RbNO 3 ) were added, and 0.74 g of nitric acid (HNO 3 ) was added. Then, the mixture was mixed to prepare a mixed solution of Bi, Co, Fe, Ni, K, Ce, Mg, and Rb precursors.
상기 Mo 전구체 용액; 및 상기 Bi, Co, Fe, Ni, K, Ce, Mg, 및 Rb 전구체 혼합 용액을 혼합하여, Mo, Bi, Fe, Co, 및 K의 전구체 혼합 용액을 완성하였다.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.
상기 전구체 혼합 용액에서, 증류수의 총량은 18.45 g이다.In the precursor mixture solution, the total amount of distilled water is 18.45 g.
(2) 플로필렌의 암모산화 공정(2) Process of ammoxidation of flophyllene
또한, 실시예 1의 촉매 대신 비교예 5의 촉매를 사용하여 플로필렌의 암모산화 공정을 수행한 뒤 그 생성물을 회수하고, 실시예 1과 마찬가지로 분석을 실시하였다.In addition, after performing the ammoxidation process of flophyllene using the catalyst of Comparative Example 5 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
상기 표 1에서, Mo는 (NH
4)
6Mo
7O
24이고, Bi는 Bi(NO
3)
3·5H
2O이고, Co는 Co(NO
3)
2·6H
2O 이고, Fe는 Fe(NO
3)
2·9H
2O이고, K는 KNO
3이다. 또한, 생략된 단위는 g이다.In Table 1, 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, and Fe is Fe( NO 3 ) 2 ·9H 2 O, and K is KNO 3 . Also, the omitted unit is g.
한편, 이종 금속 전구체 용액에 다수의 물질이 첨가된 비교예 5는, 편의상 상기 표 1에서 생략하였다.Meanwhile, Comparative Example 5 in which a number of substances were added to the dissimilar metal precursor solution was omitted from Table 1 for convenience.
실험예 1: 촉매 분석Experimental Example 1: Catalyst Analysis
다음과 같은 분석법에 따라, 실시예 및 비교예의 각 촉매를 분석하고, 그 결과를 표 3에 나타내었다:According to the following analysis method, each catalyst of Examples and Comparative Examples was analyzed, and the results are shown in Table 3:
D10, D50 및 D90의 측정: Dv은 레이저 회절법(laser diffraction method)을 이용하여 측정할 수 있다. 구체적으로, 레이저 회절법을 이용하는 입도 측정 장치(Microtrac, Blue wave)에 실시예 및 비교예의 각 촉매를 도입하여 입자들이 레이저빔을 통과할 때 입자 크기에 따른 회절패턴 차이를 측정하여 입도 분포를 산출한다. 측정 장치 내에서, 입경에 따른 부피 누적 분포의 10%, 50% 및 90%가 되는 지점에서의 입자 직경을 산출함으로써, D10, D50 및 D90의 값을 얻고, 입도 분포도((D90-D10)/D50의 값)도 출력할 수 있다. Measurement of D10, D50 and D90 : 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.
내마모성: ASTM9797-00 법을 기반으로 하여, 내경 35mm이고 높이 710mm인 수직형 내관에 50g의 촉매(W0)를 충진한 후, 10L/min으로 N2가스를 흘린 다음, 5시간 후 미분 필터에 포집된 촉매의 양(W)을 측정하여, 아래의 식을 이용하여 내마모성을 측정하였다. 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.
내마모성 (%) = (W-W0)/WWear resistance (%) = (W-W0)/W
비교예의 촉매는, 공침과 분무 건조를 통해 제조되어, 후처리로써 분급 공정이 불가피할 정도로 넓은 입도 분포를 나타낸다. 구체적으로, 비교예의 촉매는, (D90-D10)/D50의 값이 2 이상이다.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. Specifically, in the catalyst of the comparative example, the value of (D90-D10)/D50 is 2 or more.
그에 반면, 실시예의 촉매는, 실리카 담체에 금속 전구체 용액을 담지한 뒤 용매를 제거하고 소성하는 일련의 공정을 통해 제조됨에 따라, 별도 분급 공정 없이도 균일한 입도 분포를 나타낸다. 구체적으로, 실시예의 촉매는, (D90-D10)/D50의 값이 1.5 이하, 구체적으로 1.0 이하이다.On the other hand, 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. Specifically, the catalyst of Examples has a value of (D90-D10)/D50 of 1.5 or less, specifically 1.0 or less.
표 3에 따르면, 공침과 분무 건조를 통해 비교예 1의 촉매와의 관계에서, 실시예 1 내지 7의 촉매를 제조하는 데 이용된 함침법은, 내마모성이 우수한 촉매를 균일한 입도로 제조하는 데 유리한 방법임을 알 수 있다.According to Table 3, in the relationship with the catalyst of Comparative Example 1 through co-precipitation and spray drying, the impregnation method used to prepare the catalysts of Examples 1 to 7 was used to prepare a catalyst having excellent wear resistance in a uniform particle size. It can be seen that this is an advantageous method.
여기서, 비교예 1의 촉매는, 공침과 분무 건조를 통해 제조된 결과, 후처리(예컨대, 분급 공정)이 불가피할 정도로 넓은 입도 분포를 나타낸다. 그에 반면, 실시예 1 내지 7의 촉매는, 함침법을 통해 제조됨에 따라, 별도 분급 공정 없이도 균일한 입도 분포를 나타낸다.Here, 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. On the other hand, since the catalysts of Examples 1 to 7 were prepared through the impregnation method, they exhibited uniform particle size distribution without a separate classification process.
한편, 비교예 2 및 3의 촉매는, 함침법을 통해 제조되었음에도 불구하고, D50 입경이 상기 일 구현예에서 특정하는 범위(즉, 30 내지 200 ㎛)를 만족하지 못하며, 입도 분포 및 내마모성이 비교예 1보다도 열등한 수준이다.On the other hand, 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 μm) specified in the above embodiment, and the particle size distribution and abrasion resistance are compared. It is inferior to Example 1.
구체적으로, 비교예 2의 경우, D50 입경이 지나치게 작은 담체를 사용함에 따라, 이처럼 작은 입경의 담체에 활성 성분이 불충분하게 함침되어, 최종 촉매의 D50 입경이 상기 일 구현예에서 특정하는 범위의 하한에 미달하고, 입도 분포 및 내마모성이 열등해진 것으로 추론된다.Specifically, in the case of Comparative Example 2, as a carrier having an excessively small D50 particle diameter was used, the active ingredient was insufficiently impregnated in the carrier having such a small particle diameter, so that the D50 particle diameter of the final catalyst was the lower limit of the range specified in the above embodiment. It is inferred that the particle size distribution and wear resistance became inferior.
또한, 비교예 3의 경우, D50 입경이 지나치게 큰 담체를 사용함에 따라, 이처럼 큰 입경의 담체에 활성 성분이 불균일하게 함침되어, 최종 촉매의 D50 입경이 상기 일 구현예에서 특정하는 범위의 상한을 초과하고, 입도 분포 및 내마모성이 열등해진 것으로 추론된다.In addition, in the case of Comparative Example 3, as a carrier having an excessively large D50 particle diameter was used, the active ingredient was unevenly impregnated into the carrier having such a large particle diameter, so that the D50 particle diameter of the final catalyst was the upper limit of the range specified in the above embodiment Exceeded, and it is inferred that the particle size distribution and wear resistance became inferior.
이와 달리, 비교예 4 및 5의 촉매는, 함침법을 통해 제조되고, D50 입경이 상기 일 구현예에서 특정하는 범위(즉, 30 내지 200 ㎛)를 만족함에도 불구하고, 활성 금속에 의한 영향으로, 입도 분포 및 내마모성이 비교예 1와 동등하거나 그보다도 열등한 수준이다.In contrast, 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 μm) 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.
비교예 4의 경우, 활성 금속으로 Mo 및 Bi만 포함하는 금속 산화물의 영향으로, 담체에 활성 성분이 불충분하게 함침되어 최종 촉매의 입도 분포 및 내마모성이 열등해진 것으로 추론된다.In the case of Comparative Example 4, it is inferred that due to the influence of a metal oxide containing only Mo and Bi as active metals, the active ingredient is insufficiently impregnated into the carrier, resulting in inferior particle size distribution and wear resistance of the final catalyst.
또한, 비교예 5의 경우, 활성 금속으로 Mo 및 Bi뿐만 아니라 다수의 활성 금속(즉, Ce, Fe, Ni, Co, Mg, K, 및 Rb)를 포함함에 따라, 담체에 활성 성분이 불균일하게 함침되어 입도 분포 및 내마모성이 비교예 1과 동등 수준에 머무른 것으로 추론된다.In addition, in the case of Comparative Example 5, as 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.
실험예 2: 프로필렌의 암모산화 생성물 분석Experimental Example 2: Analysis of ammoxidation product of propylene
FID(Flame Ionization Detector와 TCD(Thermal conductivity detector)가 장착된 크로마토그래피(Gas chromatography, 제조사: Agilent 기기명: HP 6890 N)를 사용하여, 실시예 및 비교예의 각 암모산화 생성물을 분석하였다.Using FID (Flame Ionization Detector and TCD (thermal conductivity detector) equipped chromatography (Gas chromatography, manufacturer: Agilent instrument name: HP 6890 N), each ammoxidation product of Examples and Comparative Examples was analyzed.
구체적으로, FID로는 에틸렌(ehthlene), 사이안화수소(hydrogen cyanide), 아세트알데하이드(Acetaldehyde), 아세토니트릴(Acetonitrile), 아세토니트릴(Acrylonitrile) 등의 생성물을 분석하였으며, TCD로는 NH
3, O
2, CO, CO
2 등의 가스 생성물 및 미반응 프로필렌을 분석하여, 실시예 및 비교예에서 각각 반응한 프로필렌의 몰수와 암모산화 생성물의 몰수를 구하였다.Specifically, as 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.
이에 따른 분석 결과와 더불어 공급된 프로필렌의 몰수를 하기 1, 2, 및 3에 대입하여, 프로필렌의 전환율, 프로필렌의 암모산화 반응 생성물인 아크릴로니트릴의 선택도 및 수율을 계산하고, 그 계산값을 표 4에 기재하였다.By substituting the number of moles of propylene supplied in addition to the analysis results according to the following 1, 2, and 3, the conversion of propylene, the selectivity and yield of acrylonitrile, a product of the ammoxidation reaction of propylene, were calculated, and the calculated value was calculated. It is described in Table 4.
[식 1][Equation 1]
[식 2][Equation 2]
[식 3][Equation 3]
비교예 1의 촉매는, 공침과 분무 건조를 통해 제조된 결과, 내부 기공이 거의 포함되지 않아, 반응에 참여할 수 있는 부위가 외부 표면부로 제한된다.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.
더욱이, 비교예 1의 촉매는 입도 분포가 불균일하므로, 이를 촉매를 분급하지 않고 프로필렌의 암모산화 공정에 적용할 경우 촉매 효율과 반응성이 낮다. 또한, 비교예 1의 촉매는 마찰에 취약한 2차 입자 구조를 가지므로, 유동층 반응기 내에서 프로필렌의 암모산화 반응 진행 중 미모되거나 손상될 수 있다. 이에, 반응 중 지속적으로 촉매를 추가 공급하지 않는 한, 프로필렌의 전환율 및 아크릴로니트릴의 수율이 낮아질 수 밖에 없다.Moreover, 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.
실제로, 표 2에 따르면, 반응 중 촉매의 추가 공급 없이, 비교예 1의 촉매를 사용한 반응 시, 프로필렌의 전환율은 25 %이고, 아크릴로니트릴의 수율이 9 %에 불과한 것으로 확인된다.In fact, according to Table 2, it was confirmed that the conversion of propylene was 25% and the yield of acrylonitrile was only 9% when the reaction using the catalyst of Comparative Example 1 without additional supply of the catalyst during the reaction.
한편, 비교예 2 내지 5의 촉매는, 입도 분포와 내마모성이 비교예 1과 동등 수준이거나 그보다 열등하지만, 함침법으로 제조된 구조 상 비교예 1보다는 반응에 참여할 수 있는 유효 표면적이 넓고, 이에 따라 프로필렌의 전환율 및 아크릴로니트릴의 수율을 비교예 1보다는 개선할 수 있다.On the other hand, 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.
다만, 비교예 2 및 3의 촉매는, 상기 일 구현예에서 특정하는 D50 입경 및 입도 분포(즉, D50 입경: 30 내지 200 ㎛, 입도 분포: (D90-D10)/D50
< 2.0)를 만족하지 못하며, 실시예 1 내지 7에 대비하여 프로필렌의 전환율 및 아크릴로니트릴의 수율이 낮다.However, 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 μm, 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.
또한, 비교예 4의 촉매는, 상기 일 구현예에서 특정하는 입도 분포(즉, 입도 분포: (D90-D10)/D50
< 2.0)를 만족하지 못하며, 활성 금속으로 Mo 및 Bi만 포함하는 금속 산화물의 영향으로, 실시예 1 내지 7보다 프로필렌의 전환율과 아크릴로니트릴의 수율이 열등하다.In addition, 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.
비교예 5의 촉매는, 상기 일 구현예에서 특정하는 입도 분포(즉, 입도 분포: (D90-D10)/D50
< 2.0)를 만족하지 못하며, 활성 금속으로 Mo 및 Bi뿐만 아니라 Ce, Fe, Ni, Co, Mg, K, 및 Rb를 포함하여 지나치게 밀도가 높은 활성점이 형성된 것에 의한 영향으로, 실시예 1 내지 7보다 프로필렌의 전환율과 아크릴로니트릴의 수율이 열등하다.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.
그에 반면, 실시예 1 내지 7의 촉매는, 함침법으로 제조된 구조 상 비교예 1보다는 반응에 참여할 수 있는 유효 표면적이 넓을 뿐만 아니라, 상기 일 구현예에서 특정하는 D50 입경 및 입도 분포(즉, D50 입경: 30 내지 200 ㎛, 입도 분포: (D90-D10)/D50
< 2.0)를 만족하며, 금속 산화물 조성이 전술한 화학식 1을 만족함에 따라, 프로필렌의 전환율과 아크릴로니트릴의 수율을 현저히 개선한 것으로 평가된다.On the other hand, 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 μm, 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.
이와 같은 실시예 1 내지 7의 촉매를 참고하여, 상기 일 구현예에서 특정된 범위 내에서 촉매의 D50 입경 및 입도 분포, 금속 산화물 조성 등을 조절하여, 프로필렌의 전환율 및 아크릴로니트릴의 수율을 더욱 개선하는 것도 가능할 것이다.With reference to the catalysts of Examples 1 to 7 as described above, 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.
Claims (18)
- 하기 화학식 1로 표시되는 금속 산화물이 실리카 담체에 담지된 촉매이고,The metal oxide represented by the following formula (1) is a catalyst supported on a silica carrier,상기 촉매는,The catalyst,D50 입경이 30 내지 300 ㎛이고,The D50 particle diameter is 30 to 300 μm,D10 입경, D50 입경 및 D90 입경이 하기 식 1의 관계를 만족하는 것인,The D10 particle size, the D50 particle size, and the D90 particle size satisfy the relationship of Formula 1 below,프로필렌의 암모산화용 촉매:Catalyst for ammoxidation of propylene:[식 1][Equation 1][화학식 1][Formula 1]상기 화학식 1에서,In Formula 1,A 는 Ni, Mn, Co, Zn, Mg, Ca, 및 Ba 중 하나 이상의 원소이고,A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,B는 Li, Na, K, Rb, 및 Cs 중 하나 이상의 원소이고,B is one or more elements of Li, Na, K, Rb, and Cs,C는 Cr, W, B, Al, Ca, 및 V 중 하나 이상의 원소이고,C is one or more elements of Cr, W, B, Al, Ca, and V, and상기 a 내지 e, 및 x는 각각 원자 또는 원자단의 분율이며, a는 0.1 내지 5이고, b는 0.1 내지 5 이고, c는 0.01 내지 10이고, d는 0.01 내지 2이며, e는 0 내지 10이고, x는 24 내지 48이다.Wherein 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.
- 제1항에 있어서,The method of claim 1,상기 촉매는,The catalyst,제2 기공을 포함하는 실리카 담체;A silica carrier including second pores;상기 제2 기공의 벽면을 연속적으로 코팅하고, 상기 화학식 1로 표시되는 금속 산화물을 포함하는 내부 코팅층; 및An inner coating layer that continuously coats the walls of the second pores and includes a metal oxide represented by Chemical Formula 1; And상기 제2 기공 내부에 위치하고, 상기 내부 코팅층을 제외한 빈 공간을 차지하는 제1 기공;을 포함하는 것인,Including; first pores located inside the second pores and occupying an empty space excluding the inner coating layer프로필렌의 암모산화용 촉매.Catalyst for ammoxidation of propylene.
- 제1항에 있어서,The method of claim 1,상기 촉매는,The catalyst,D50 입경이 45 내지 200 ㎛인 것인,The D50 particle diameter is 45 to 200 ㎛,프로필렌의 암모산화용 촉매.Catalyst for ammoxidation of propylene.
- 제1항에 있어서,The method of claim 1,상기 금속 산화물은,The metal oxide,하기 화학식 1-1로 표시되는 것인,It is represented by the following formula 1-1,프로필렌의 암모산화용 촉매:Catalyst for ammoxidation of propylene:[화학식 1-1][Formula 1-1]상기 화학식 1-1에서, a 내지 d 및 x의 각 정의는 제1항과 같다.In Formula 1-1, each definition of a to d and x is the same as in claim 1.
- 제1항에 있어서,The method of claim 1,상기 금속 산화물 및 상기 실리카 담체의 중량비가 15:85 내지 35:65인 것인,The weight ratio of the metal oxide and the silica carrier is 15:85 to 35:65,프로필렌의 암모산화용 촉매.Catalyst for ammoxidation of propylene.
- 제1항에 있어서,The method of claim 1,상기 촉매는,The catalyst,ASTM9797-00 에 따라, 내경 35 mm이고 높이 710 mm인 수직형 내관에 50g의 촉매(W0)를 충진한 후, 10 L/min으로 N 2 가스를 흘린 다음, 5시간 후 미분 필터에 포집된 촉매의 양(W)을 측정하여, 하기 식을 이용하여 계산된 마모 손실(Attrition loss)이 9 % 이하인 것인,According to ASTM9797-00, after 50g of catalyst (W0) was filled in a vertical inner tube with an inner diameter of 35 mm and a height of 710 mm, N 2 gas was flowed at 10 L/min, and then the catalyst collected in the fine filter after 5 hours. By measuring the amount (W) of, the attrition loss calculated using the following equation is 9% or less,프로필렌의 암모산화용 촉매:Catalyst for ammoxidation of propylene:마모 손실 (%) = (W-W0)/WWear loss (%) = (W-W0)/W
- 구연산, 옥살산, 또는 이들의 혼합물인 첨가제; 및 Mo 전구체를 포함하는 제1 전구체 용액을 제조하는 단계,Additives that are citric acid, oxalic acid, or mixtures thereof; And preparing a first precursor solution including a Mo precursor,Bi 전구체, Fe 전구체, A 전구체(A= Ni, Mn, Co, Zn, Mg, Ca, 및 Ba 중 하나 이상의 원소), 및 B 전구체(B= Li, Na, K, Rb, 및 Cs 중 하나 이상의 원소)를 포함하는 제2 전구체 용액을 제조하는 단계,Bi precursor, Fe precursor, A precursor (A = one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba), and B precursor (B = one or more of Li, Na, K, Rb, and Cs Element) preparing a second precursor solution,금속의 몰비가 하기 화학식 1의 화학양론적 몰비를 만족하도록 하며, 상기 제1 및 제2 전구체 용액을 혼합하는 단계,Mixing the first and second precursor solutions so that the molar ratio of the metal satisfies the stoichiometric molar ratio of Formula 1 below,상기 제1 및 제2 전구체 용액의 혼합물을 실리카 담체에 담지시키는 단계,Supporting the mixture of the first and second precursor solutions on a silica carrier,상기 제1 및 제2 전구체 용액의 혼합물이 담지된 실리카 담체를 건조시키는 단계, 그리고Drying the silica carrier on which the mixture of the first and second precursor solutions is supported, and상기 건조된 물질을 소성하는 단계를 포함하는,Comprising the step of firing the dried material,프로필렌의 암모산화용 촉매의 제조 방법:Method for producing a catalyst for ammoxidation of propylene:[화학식 1][Formula 1]상기 화학식 1에서,In Formula 1,A 는 Ni, Mn, Co, Zn, Mg, Ca, 및 Ba 중 하나 이상의 원소이고,A is one or more elements of Ni, Mn, Co, Zn, Mg, Ca, and Ba,B는 Li, Na, K, Rb, 및 Cs 중 하나 이상의 원소이고,B is one or more elements of Li, Na, K, Rb, and Cs,C는 Cr, W, B, Al, Ca, 및 V 중 하나 이상의 원소이고,C is one or more elements of Cr, W, B, Al, Ca, and V, and상기 a 내지 e, 및 x는 원자 또는 원자단의 분율이며, a는 0.1 내지 5이고, b는 0.1 내지 5 이고, c는 0.01 내지 10이고, d는 0.01 내지 2이며, e는 0 내지 10이고, x는 24 내지 48이다.Wherein 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.
- 제8항에 있어서,The method of claim 8,상기 제1 전구체 용액을 제조하는 단계에서,In the step of preparing the first precursor solution,상기 Mo 전구체 및 상기 첨가제의 중량비는, 1:0.1 내지 1:1를 만족하도록 하는 것인,The weight ratio of the Mo precursor and the additive is to satisfy 1:0.1 to 1:1,프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 제8항에 있어서,The method of claim 8,상기 제2 전구체 용액을 제조하는 단계에서,In the step of preparing the second precursor solution,C 전구체(Cr, W, B, Al, Ca, 및 V 중 하나 이상의 원소)를 더 포함하는 제2 전구체 용액을 제조하는 것인,To prepare a second precursor solution further comprising a C precursor (at least one element of Cr, W, B, Al, Ca, and V),프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 제8항에 있어서,The method of claim 8,상기 제2 전구체 용액을 제조하는 단계에서,In the step of preparing the second precursor solution,Bi 전구체, Fe 전구체, Co 전구체, 및 K 전구체를 포함하는 제2 전구체 용액을 제조하는 것인,To prepare a second precursor solution comprising a Bi precursor, a Fe precursor, a Co precursor, and a K precursor,프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 제8항에 있어서,The method of claim 8,상기 제1 및 제2 전구체 용액의 혼합물이 담지된 실리카 담체를 건조시키는 단계는,Drying the silica carrier on which the mixture of the first and second precursor solutions is supported,상기 제1 및 제2 전구체 용액의 혼합물이 담지된 실리카 담체를 120 내지 160 mbar에서 1차 진공 건조하는 단계, 및First vacuum drying the silica carrier on which the mixture of the first and second precursor solutions is supported at 120 to 160 mbar, and상기 1차 진공 건조된 물질을 30 내지 50 mbar에서 2차 진공 건조하여, 상기 제1 및 제2 전구체 용액의 혼합물이 담지된 실리카 담체를 수득하는 단계를 포함하는 것인,Including the step of obtaining a silica carrier on which the mixture of the first and second precursor solutions is supported by secondary vacuum drying the first vacuum-dried material at 30 to 50 mbar,프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 제12항에 있어서,The method of claim 12,상기 1차 진공 건조는,The primary vacuum drying,60 내지 80 ℃에서 수행되는 것인,That is carried out at 60 to 80 °C,프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 제12항에 있어서,The method of claim 12,상기 2차 진공 건조는,The second vacuum drying,80 내지 100 ℃에서 수행되는 것인,That is carried out at 80 to 100 °C,프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 제12항에 있어서,The method of claim 12,상기 2차 진공 건조된 물질을 상압에서 3차 건조하는 단계;를 더 포함하는 것인,The second vacuum-dried material is thirdly dried at normal pressure; which further comprises,프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 제15항에 있어서,The method of claim 15,상기 3차 건조는,The third drying,100 내지 120 ℃에서 수행되는 것인,That is carried out at 100 to 120 °C,프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 제8항에 있어서,The method of claim 8,상기 건조된 물질을 소성하는 단계는,The step of firing the dried material,500 내지 700 ℃에서 수행되는 것인,Which is carried out at 500 to 700 °C,프로필렌의 암모산화용 촉매의 제조 방법.Method for producing a catalyst for ammoxidation of propylene.
- 반응기 내에서, 제1항의 촉매 존재 하에 프로필렌 및 암모니아를 반응시키는 단계를 포함하는,In the reactor, comprising the step of reacting propylene and ammonia in the presence of the catalyst of claim 1,프로필렌의 암모산화 방법.Method for ammoxidation of propylene.
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JP2021522080A JP7161614B2 (en) | 2019-09-30 | 2020-09-25 | Catalyst for ammoxidation of propylene, method for producing the same, and method for ammoxidation of propylene using the same |
EP20872266.0A EP3974058A4 (en) | 2019-09-30 | 2020-09-25 | Catalyst for ammoxidation of propylene, method for preparing same, and method for ammoxidation of propylene using same |
CN202080006347.0A CN113164928A (en) | 2019-09-30 | 2020-09-25 | Ammoxidation catalyst for propylene, process for producing the catalyst, and ammoxidation method using the catalyst |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60166037A (en) * | 1984-02-07 | 1985-08-29 | Nitto Chem Ind Co Ltd | Manufacture of oxide catalyst containing antimony deposited on silica |
KR100687671B1 (en) * | 2003-03-05 | 2007-03-02 | 아사히 가세이 케미칼즈 가부시키가이샤 | Particulate Porous Ammoxidation Catalyst |
WO2011119203A1 (en) * | 2010-03-23 | 2011-09-29 | Ineos Usa Llc | High efficiency ammoxidation process and mixed metal oxide catalysts |
KR101537459B1 (en) * | 2011-04-21 | 2015-07-16 | 아사히 가세이 케미칼즈 가부시키가이샤 | Silica-loaded catalyst |
KR20160066922A (en) * | 2014-12-03 | 2016-06-13 | 주식회사 엘지화학 | Multi-component complex metal oxides catalyst, method for preparing the same, and method for preparing 1,3-butadiene using the same |
-
2020
- 2020-09-25 WO PCT/KR2020/013098 patent/WO2021066410A1/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60166037A (en) * | 1984-02-07 | 1985-08-29 | Nitto Chem Ind Co Ltd | Manufacture of oxide catalyst containing antimony deposited on silica |
KR100687671B1 (en) * | 2003-03-05 | 2007-03-02 | 아사히 가세이 케미칼즈 가부시키가이샤 | Particulate Porous Ammoxidation Catalyst |
WO2011119203A1 (en) * | 2010-03-23 | 2011-09-29 | Ineos Usa Llc | High efficiency ammoxidation process and mixed metal oxide catalysts |
KR101537459B1 (en) * | 2011-04-21 | 2015-07-16 | 아사히 가세이 케미칼즈 가부시키가이샤 | Silica-loaded catalyst |
KR20160066922A (en) * | 2014-12-03 | 2016-06-13 | 주식회사 엘지화학 | Multi-component complex metal oxides catalyst, method for preparing the same, and method for preparing 1,3-butadiene using the same |
Non-Patent Citations (1)
Title |
---|
See also references of EP3974058A4 * |
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