Title of Invention: Catalyst for ammoxidation of propylene, method for producing same, method for ammoxidation of propylene using same
technical field
[One]
Cross-Citation with Related Application(s)
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0094652 on July 29, 2020 and Korean Patent Application No. 10-2021-0099864 on July 29, 2021, All content disclosed in the literature is incorporated as a part of this specification.
[3]
The present invention relates to a catalyst for ammoxidation of propylene, a method for producing the same, and a method for ammoxidation of propylene using the same.
[4]
background
[5]
Acrylonitrile (AN) is not only used as one of the raw materials of ABS resin, but also can be applied to various chemical products, so demand and production are increasing worldwide.
[6]
Such acrylonitrile can be prepared through the ammoxidation reaction of propylene. The ammoxidation reaction of propylene includes a reduction reaction of ammonia and propylene and a reoxidation reaction by oxygen, and a fluidized bed reactor is generally used to control heat generated during these reactions.
[7]
As a catalyst for ammoxidation of propylene, since Mo (molybdenum)-Bi (bismuth) oxide catalysts have been proposed, catalysts to which metals having various oxidation states are added have been proposed. However, despite the diversification of the catalyst composition, research on the structure and physical properties thereof is insufficient, and there is a limit in increasing the yield of acrylonitrile.
[8]
Specifically, the sol-gel method is widely known as a method for preparing a catalyst for ammoxidation of propylene, which corresponds to a method in which a metal precursor solution and silica sol are co-precipitated, and the co-precipitation product is spray-dried and then calcined.
[9]
According to this sol-gel method, a catalyst having a secondary particle structure in which metal oxide particles and silica particles are aggregated is prepared. The binding force of the primary particles constituting the secondary particles is weak, so that they are worn out in the fluid reactor or split into primary particles. It is easy to lose catalytic activity. Moreover, since the sites that can participate in the ammoxidation reaction of propylene are limited to the outer surface portion (i.e., the surface of secondary particles) and provide a small surface area, the amount of ammonia desorbed from the catalyst surface during the ammoxidation reaction of propylene is many. In addition, the metal oxide component (particularly, Mo) is easily eluted and volatilized at a high temperature (about 400 to 600 ° C.) where the ammoxidation reaction of propylene proceeds, and thus the catalyst performance is easily reduced.
[10]
Therefore, when using the catalyst prepared by the sol-gel method, it is necessary to continuously add the catalyst (make-up) during the ammoxidation reaction of propylene, and even if it is added, there is a limit in increasing the yield of acrylonitrile.
[11]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
The present invention provides a catalyst for ammoxidation of propylene that minimizes metal oxide components (especially, Mo) eluted and volatilized from the catalyst during ammoxidation reaction of propylene, and using this catalyst, acrylonitrile is produced in a higher yield is for manufacturing.
[13]
means of solving the problem
[14]
Specifically, in one embodiment of the present invention, a catalyst for ammoxidation of propylene having a structure in which a molybdenum (Mo) oxide is first supported and a heterogeneous metal oxide including bismuth (Bi) is supported later, and a method for preparing the same provides
[15]
A catalyst for ammoxidation of propylene according to an embodiment of the present invention includes a silica carrier; and a metal oxide supported on the silica carrier,
[16]
The metal oxide, but the overall composition satisfies the following formula (1),
[17]
a coating layer comprising molybdenum (Mo) oxide; and one or more coating layers positioned on the coating layer including the molybdenum (Mo) oxide and including a dissimilar metal; may include:
[18]
[Formula 1]
[19]
Mo 12 Bi a Fe b A c B d C e D F O x
[20]
In Formula 1,
[21]
A is at least one element of Ni, Mn, and Co,
[22]
B is one or more elements of Zn, Mg, Ca, and Ba;
[23]
C is one or more of Li, Na, K, Rb, and Cs,
[24]
D is one or more of Cr, W, B, Al, Ca, and V,
[25]
Wherein a to f and x are each a fraction of an atom or group, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 10, and e is 0.01 to 2; , f is 0 to 10, and x is 24 to 48.
[26]
The catalyst for ammoxidation of propylene may be prepared by, for example, a manufacturing method comprising the following steps:
[27]
preparing a first catalyst by supporting molybdenum (Mo) oxide on a silica carrier; and
[28]
A step of supporting an oxide of a heterogeneous metal on the first catalyst to obtain a catalyst in which the metal oxide is supported on a silica carrier.
[29]
Effects of the Invention
[30]
In the catalyst of one embodiment, the elution of molybdenum (Mo) during the ammoxidation reaction of propylene is suppressed and the catalytic performance is reduced by a structure in which molybdenum (Mo) oxide is supported first, and a heterogeneous metal oxide is supported later. can be maintained
[31]
Therefore, when using the catalyst of one embodiment, acrylonitrile can be mass-produced in high yield without additional supply of catalyst during the ammoxidation process of propylene in the fluidized bed reactor.
[32]
Brief description of the drawing
[33]
1 schematically shows a catalyst prepared using a sol-gel method.
[34]
2 schematically shows a catalyst according to the embodiment.
[35]
Modes for carrying out the invention
[36]
Since the present invention can apply various transformations and can have various embodiments, specific embodiments will be illustrated and described in detail. However, this is not intended to limit the present invention to specific embodiments, and it should be understood that all modifications, equivalents and substitutes included in the spirit and scope of the present invention are included. In describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.
[37]
In addition, terms including ordinal numbers such as first, second, etc. to be used below 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. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.
[38]
The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.
[39]
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 size at the 50% point of the cumulative volume distribution according to the particle size, D90 is the particle size at the 90% point of the cumulative volume distribution according to the particle size, and D10 is the particle size at the 10% point of the cumulative volume distribution according to the particle size. to be.
[40]
In addition, "pore diameter" may mean the length of a straight line passing through the center of the pore. In addition, the silica carrier may include a plurality of pores, and in this case, the average diameter may be obtained by arithmetic average of the diameters of the plurality of pores. Alternatively, the pore diameter and the average pore diameter can be obtained by the Barrett-Joyner-Halenda (BJH) method from the desorption isotherm of nitrogen gas under the liquid nitrogen temperature.
[41]
Meanwhile, in the initial stage of the catalytic reaction, a process in which reactants are chemically adsorbed on the catalyst surface is required, and the active point and surface area of ​​the catalyst are directly related to the adsorption capacity and the resulting chemical reaction. Also, chemisorption on the catalyst surface tends to increase with increasing temperature, although the rate of adsorption is slower than that of physisorption.
[42]
In this regard , the ammonia temperature elevated desorption method (NH 3 -TPD) , which measures the degree of the acid site strength of the catalyst by the desorption degree (TPD: Temperature Programmed Desorption) of ammonia (NH 3 ) is widely known. In the present invention, the ammonia (NH 3 ) adsorption amount of the catalyst and the carrier can be measured using the ammonia temperature elevation desorption method (NH 3 -TPD).
[43]
[44]
Hereinafter, the catalyst for ammoxidation of propylene of one embodiment will be described in detail with reference to the drawings.
[45]
[46]
Catalyst for ammoxidation of propylene
[47]
[48]
In one embodiment of the present invention, there is provided a catalyst for ammoxidation of propylene having a structure in which a molybdenum (Mo) oxide is first supported, and a heterogeneous metal oxide including bismuth (Bi) is supported later.
[49]
[50]
Specifically, in the catalyst of one embodiment, the overall composition satisfies the following Chemical Formula 1, but molybdenum (Mo) is distributed in the lower part (ie, the silica carrier side), and a heterogeneous metal is a metal distributed on the lower part Oxide; this is supported on a silica carrier:
[51]
[Formula 1]
[52]
Mo 12 Bi a Fe b A c B d C e D f O x
[53]
In Formula 1,
[54]
A is at least one element of Ni, Mn, and Co,
[55]
B is one or more elements of Zn, Mg, Ca, and Ba;
[56]
C is one or more of Li, Na, K, Rb, and Cs,
[57]
D is one or more of Cr, W, B, Al, Ca, and V,
[58]
Wherein a to f and x are each a fraction of an atom or group, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 10, and e is 0.01 to 2; , f is 0 to 10, and x is 24 to 48.
[59]
[60]
A commonly known catalyst for ammoxidation of propylene is prepared by a sol-gel method and provided in a secondary particle structure in which metal oxide nanoparticles and silica nanoparticles are aggregated ( FIG. 1 ).
[61]
This is because, instead of uniformly distributed metal oxide particles inside and outside, the site that can participate in the ammoxidation reaction of propylene is limited to the outer surface portion (that is, the surface of secondary particles), and provides a small surface area, During the ammoxidation reaction, the amount of ammonia desorbed from the catalyst surface is large.
[62]
[63]
On the other hand, it may be prepared by an impregnation method, and provided in a structure in which a metal oxide is supported on a silica carrier.
[64]
The catalyst prepared by such an impregnation method may have less fine powder content and superior durability than a catalyst prepared by the sol-gel method with the same composition, even if a classification process is not performed as a post-processing after preparation.
[65]
However, when all metal precursors are supported at once, molybdenum (Mo) is not fully supported to the inside of the pores of the silica carrier, and the MoO 3 phase increases, so the volatilization or loss of molybdenum (Mo) during the ammoxidation reaction of propylene is high. .
[66]
[67]
In particular, in the catalyst of one embodiment, in order to reduce the probability of volatilization or loss of molybdenum (Mo) during the ammoxidation reaction of propylene, molybdenum (Mo) oxide is first supported on a silica carrier, and then heterogeneous (including bismuth (Bi))異 species) metal oxides are sequentially supported (FIG. 2).
[68]
Here, for sequential loading of the metal oxide, mixing with a molybdenum (Mo) metal precursor solution, drying, and firing are performed, and then mixing with a heterogeneous metal precursor including bismuth (Bi), drying, and Firing can be performed.
[69]
For example, when the silica carrier and the molybdenum (Mo) precursor solution are mixed and the solvent (ie, water) is removed through a drying process, the molybdenum (Mo) precursor remains on the pore walls of the silica carrier, and the firing process As the molybdenum (Mo) precursor is oxidized, a molybdenum (Mo) oxide film (coating layer) that continuously coats the pore walls of the silica carrier may be formed.
[70]
Thereafter, the bismuth (Bi) and heterogeneous metal oxide coating layers may be formed in the same manner as in forming the molybdenum (Mo) oxide coating layer.
[71]
[72]
In the catalyst of one embodiment, the elution of molybdenum (Mo) during the ammoxidation reaction of propylene has a structure in which molybdenum (Mo) oxide is first supported and heterogeneous metal oxides including bismuth (Bi) are supported later. suppressed and catalytic performance can be maintained.
[73]
Therefore, when using the catalyst of one embodiment, acrylonitrile can be mass-produced in high yield without additional supply of catalyst during the ammoxidation process of propylene in the fluidized bed reactor.
[74]
[75]
In addition, the catalyst of one embodiment is a catalyst by controlling the metal oxide composition to further include a metal that forms an active site at a suitable level for the ammoxidation reaction of propylene, as well as Mo and Bi, which are known to increase the activity of the ammoxidation reaction. activity can be further increased.
[76]
[77]
Hereinafter, the catalyst of the embodiment will be described in more detail.
[78]
[79]
Structure of metal oxide
[80]
[81]
As described above, in the catalyst of one embodiment, as the metal oxide is divided and supported two or more times, molybdenum (Mo) is distributed in the lower part, and bismuth (Bi) and the dissimilar metal are distributed in the upper part. Metal oxide; may have a structure supported on the silica carrier.
[82]
[83]
Specifically, the metal oxide may include a coating layer including molybdenum (Mo) oxide; and one or more coating layers positioned on the coating layer including the molybdenum (Mo) oxide and including a dissimilar metal.
[84]
For example, the metal oxide supported by dividing it into two times may include a first coating layer including molybdenum (Mo) oxide; and bismuth (Bi), iron (Fe), element A (A = at least one of Ni, Mn, and Co), element B (B = among Zn, Mg, Ca, and Ba), located on the first coating layer. one or more elements), and a second coating layer comprising an oxide of element C (C=at least one of Li, Na, K, Rb, and Cs).
[85]
On the other hand, the metal oxide supported by dividing into three times may include a first coating layer including molybdenum (Mo) oxide; and a second coating layer disposed on the first coating layer and including oxides of bismuth (Bi) and iron (Fe); and Element A (A=at least one of Ni, Mn, and Co), Element B (B=at least one of Zn, Mg, Ca, and Ba), and Element C (C) located on the second coating layer = Li, Na, K, Rb, and a third coating layer comprising an oxide of Cs); may include.
[86]
In addition, the metal oxide supported by dividing into four times, a first coating layer containing molybdenum (Mo) oxide; and a second coating layer disposed on the first coating layer and including bismuth (Bi) oxide. a third coating layer positioned on the second coating layer and including iron (Fe) oxide; and Element A (A=at least one of Ni, Mn, and Co), Element B (B=at least one of Zn, Mg, Ca, and Ba), and Element C (C) located on the third coating layer = Li, Na, K, Rb, and a fourth coating layer comprising an oxide of Cs); may include.
[87]
However, in any structure, the overall composition of the coating layers satisfies Chemical Formula 1, and the metals on the upper and lower portions of the adjacent coating layers may be chemically bonded to each other.
[88]
For example, molybdenum (Mo) of the first coating layer may exist in the form of MoO 3 , but it is also combined with bismuth (Bi) of the second coating layer adjacent thereto to form a Mo-Bi-O bond, and molybdenum during the ammoxidation reaction of propylene. The probability of volatilization or loss of (Mo) may be reduced.
[89]
[90]
Composition of metal oxides
[91]
[92]
On the other hand, even if it has the same structure as the catalyst of the one embodiment, if the type and content of the components constituting the metal oxide do not satisfy Formula 1 above, the active point of the catalyst insufficient or too dense for ammoxidation of propylene is formed can be
[93]
Accordingly, the type and content of elements constituting the metal oxide need to satisfy Chemical Formula 1 above.
[94]
In particular, when the metal oxide is represented by the following Chemical Formula 1-1, the effect of increasing the conversion rate by increasing the movement rate of lattice oxygen of molybdenum of Fe, partial oxidation reaction characteristics of propylene by forming a complex oxide of Ni and Zn with molybdenum With the synergistic effect of increasing the AN selectivity by dispersing the active points of the complex oxide containing molybdenum of K and increasing the AN selectivity, the activity in the ammoxidation reaction of propylene can be higher:
[95]
[Formula 1-1]
[96]
Mo 12 Bi a Fe b Ni c Zn d K e O x
[97]
In Formula 1-1, a to e and x are each an atom or 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 10, specifically 1 to 10, e is 0.01 to 2, specifically 0.01 to 1.0, and x is 24-48, specifically It may be 28 to 45 days.
[98]
[99]
Metal oxide: weight ratio of carrier
[100]
[101]
The catalyst of one embodiment may include the metal oxide and the silica carrier in a weight ratio of 15:85 to 35:65, specifically 20:80 to 35:65 (metal oxide:silica carrier).
[102]
Within this range, the catalyst of one embodiment may have high selectivity of acrylonitrile with high activity.
[103]
[104]
silica carrier
[105]
[106]
The pore diameter of the silica carrier may be 4 nm to 40 nm.
[107]
Specifically, the diameter is 4 nm or more, 4.2 nm or more, 4.4 nm or more, 4.6 nm or more, 4.8 nm or more, or 5 nm or more, and 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, or 20 nm When using a silica carrier including the following pores, the catalyst exhibiting the above-described pore characteristics and ammonia adsorption amount can be implemented.
[108]
The D50 particle diameter of the silica carrier may be in the range of 50 μm to 150 μm. Specifically, the silica carrier has a lower limit of 50 μm or more, 51 μm or more, 53 μm or more, or 55 μm or more of the D50 particle size and an upper limit of 150 μm or less, 130 μm or less, 110 μm or less, or 90 μm or less. can do.
[109]
[110]
Catalyst structure
[111]
[112]
The catalyst of one embodiment may include a silica carrier including a second pore; an inner coating layer continuously coating the wall surfaces of the second pores and including the metal oxide represented by Chemical Formula 1; and a first pore positioned inside the second pore and occupying an empty space excluding the inner coating layer.
[113]
Here, the diameter of the second pores may be 4 nm to 40 nm, and the first pores may be determined according to the amount of the metal oxide supported in the second pores.
[114]
In particular, the inner coating layer, as described above, a coating layer comprising molybdenum (Mo) oxide; and one or more coating layers positioned on the coating layer including the molybdenum (Mo) oxide and including a dissimilar metal.
[115]
Due to such a supported structure, as compared to a catalyst prepared by a sol-gel method, it can be a catalyst having a small content of fine powder, excellent durability, a low elution probability of molybdenum (Mo), and high activity.
[116]
Therefore, when using the catalyst of one embodiment, acrylonitrile can be obtained in high yield without additional supply of catalyst during the ammoxidation process of propylene in the fluidized bed reactor.
[117]
[118]
Specifically, the catalyst of one embodiment may have an egg-shell structure.
[119]
For this purpose, the silica carrier includes a non-porous core portion; and a porous shell portion located on the surface of the non-porous core and including second pores having a diameter of 2 to 30 nm.
[120]
Specifically, the porous shell includes a concave portion and a convex portion of the surface, and the concave portion is formed by opening the second pores to the surface of the porous shell. it could be
[121]
Accordingly, the catalyst of one embodiment may include a coating layer that continuously coats the concave and convex portions of the porous shell and includes a metal oxide represented by Chemical Formula 1; and a first pore occupying an empty space excluding the coating layer in the main portion of the silica carrier.
[122]
[123]
In the catalyst of one embodiment, the lower limit of the D50 particle size is 30 µm or more, 35 µm or more, 40 µm or more, or 45 µm or more, and the upper limit is 200 µm or less, 190 µm or less, 180 µm or less, 170 µm or less, 160 It can be made into micrometer or less, or 150 micrometers or less.
[124]
[125]
Ammonia Adsorption Amount of Catalyst
[126]
[127]
In the initial stage of the catalytic reaction, a process in which reactants are chemically adsorbed on the catalyst surface is required, and the active site and surface area of ​​the catalyst are directly related to the adsorption capacity and the resulting chemical reaction.
[128]
Also, chemisorption on the catalyst surface tends to increase with increasing temperature, although the rate of adsorption is slower than that of physisorption.
[129]
[130]
In this regard , the ammonia temperature elevated desorption method (NH 3 -TPD) , which measures the degree of the acid site strength of the catalyst by the desorption degree (TPD: Temperature Programmed Desorption) of ammonia (NH 3 ) is widely known.
[131]
[132]
For example, after pretreatment by leaving the catalyst at 400° C. for about 1 hour, 10% NH 3 /He (50 cc/min) at about 100° C. for 1 hour to adsorb NH 3 to the catalyst, and at the same temperature While flowing He, the physically adsorbed NH 3 is removed, the temperature is raised to 800° C., and the desorbed NH 3 is measured (b). At this time, the pretreatment of the catalyst is, for example, by filling the catalyst in a device capable of measuring ammonia temperature elevation desorption method, and then using helium gas (50 cc/min) to increase the temperature from room temperature to 10° C./min. After raising the temperature to 400 °C, it can be carried out by maintaining the temperature at 400 °C for 1 hour.
[133]
Thereafter, by obtaining the difference between the initial adsorption amount (a) and the desorption amount (b) of NH 3 , the adsorption amount of NH 3 remaining on the catalyst surface can be obtained.
[134]
[135]
The catalyst of one embodiment may have an adsorption amount of ammonia measured by the above method of 0.05 mmol/g or more. As such, the catalyst having excellent ammonia adsorption capacity increases the conversion rate of propylene and the selectivity of acrylonitrile during ammoxidation of propylene, and ultimately contributes to improving the yield of acrylonitrile.
[136]
[137]
For example, the catalyst of one embodiment has an ammonia adsorption amount of 0.5 mmol/g or more, 0.53 mmol/g or more, 0.55 mmol/g or more, or 0.57 mmol/g or more, and 5 mmol/g or less, 4 mmol/g or less, 3 It may be less than or equal to mmol/g, less than or equal to 2 mmol/g, or less than or equal to 1.5 mmol/g.
[138]
[139]
Catalyst pore diameter and BET specific surface area
[140]
[141]
The catalyst of one embodiment may have a BET specific surface area of ​​100 m 2 /g or more while including pores having a diameter of 4 nm or more in a state in which a metal oxide of a specific composition is supported on a silica carrier. As a result, compared to the catalyst prepared by the sol-gel method, a site capable of adsorbing ammonia gas and propylene gas may be significantly increased.
[142]
[143]
As described above, in the catalyst prepared by the sol-gel method, the site that can participate in the ammoxidation reaction of propylene is limited to the outer surface portion (ie, the surface of secondary particles), whereas the catalyst of one embodiment is the ammoxidation of propylene. The surface area that can participate in the reaction extends not only to the outer surface (ie, the surface of the catalyst), but also to its inner surface (pores).
[144]
[145]
For example, the catalyst of one embodiment has a diameter of 4 nm or more, 4.1 nm or more, 4.2 nm or more, 4.3 nm or more, 4.4 nm or more, or 4.5 nm or more, and 40 nm or less, 35 nm or less, 30 nm or less, 25 It may include pores that are less than or equal to nm, less than or equal to 20 nm, or less than or equal to 15 nm.
[146]
In addition, the catalyst of one embodiment has a BET specific surface area of ​​100 m 2 /g or more, 120 m 2 /g or more, 140 m 2 /g or more, 160 m 2 /g or more, 170 m 2 /g or more, or 175 m 2 /g or less, 300 m 2 /g or less, 270 m 2 /g or less, 250 m 2 /g or less, 230 m 2 /g or less, or 227 m 2 /g or less.
[147]
[148]
Method for preparing a catalyst for ammoxidation of propylene
[149]
[150]
In another embodiment of the present invention, molybdenum (Mo) oxide is first supported on a silica carrier, and then a heterogeneous metal oxide is supported later, thereby providing a method for preparing the catalyst of the above-described embodiment.
[151]
[152]
Specifically, the manufacturing method of the one embodiment,
[153]
Supporting molybdenum (Mo) oxide on a silica carrier to prepare a first catalyst;
[154]
and supporting an oxide of a heterogeneous metal on the first catalyst to obtain a catalyst in which a metal oxide satisfying the following Chemical Formula 1 is supported on a silica carrier.
[155]
In this case, the metal oxide supported on the silica carrier may include a coating layer including molybdenum (Mo) oxide; and one or more coating layers positioned on the coating layer including the molybdenum (Mo) oxide and including a dissimilar metal; may include:
[156]
[Formula 1]
[157]
Mo 12 Bi a Fe b A c B d C e D f O x
[158]
In Formula 1,
[159]
A is at least one of Ni, Mn, and Co,
[160]
B is one or more elements of Zn, Mg, Ca, and Ba;
[161]
C is one or more of Li, Na, K, Rb, and Cs,
[162]
D is one or more of Cr, W, B, Al, Ca, and V,
[163]
Wherein a to f and x are each a fraction of an atom or group, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 10, and e is 0.01 to 2; , f is 0 to 10, and x is 24 to 48.
[164]
[165]
As briefly described above, for sequential loading of metal oxides, mixing with a molybdenum (Mo) metal precursor solution, drying, and firing are performed, and then mixing with a heterogeneous metal precursor including bismuth (Bi) , drying, and firing may be performed.
[166]
[167]
Hereinafter, descriptions overlapping those described above will be omitted, and each step will be described.
[168]
[169]
In the manufacturing method of the embodiment, the step of supporting the oxide of the heterogeneous metal on the first catalyst according to the number of times the metal oxide is supported may be performed as follows.
[170]
When it is intended to be supported by dividing it into Mo oxide and other metal oxides (supporting twice), the step of supporting the oxide of a heterogeneous metal on the first catalyst includes bismuth (Bi), iron (Fe) on the first catalyst. ), element A (A = one or more of Ni, Mn, and Co), element B (B = one or more of Zn, Mg, Ca, and Ba, and element C (C = Li, Na, K, Rb) , and supporting an oxide of one or more elements of Cs); may include.
[171]
On the other hand, when supported three times, the step of supporting the oxide of the dissimilar metal on the first catalyst may include oxides of bismuth (Bi) and iron (Fe) on the first catalyst; and element A (A = one or more of Ni, Mn, and Co), element B (B = one or more of Zn, Mg, Ca, and Ba), and element C (C = Li, Na, K, Rb) , and sequentially supporting an oxide of one or more elements of Cs).
[172]
When supported 4 times, bismuth (Bi) oxide on the first catalyst; iron (Fe) oxide; and element A (A = one or more of Ni, Mn, and Co), element B (B = one or more of Zn, Mg, Ca, and Ba), and element C (C = Li, Na, K, Rb) , and sequentially supporting an oxide of one or more elements of Cs).
[173]
[174]
In each of the above steps, the supporting of the metal oxide is a set of a series of processes of mixing, drying, and calcining the silica carrier or the catalyst of the previous step with the precursor solution, and depending on the desired number of supporting, two or more sets. can be composed of
[175]
For example, when supported twice, the silica carrier is mixed with a molybdenum (Mo) precursor solution, dried, and calcined to prepare a first catalyst, and then the first catalyst is mixed with bismuth (Bi), iron (Fe), element A, The final catalyst can be obtained by mixing, drying, and calcining with a mixed solution of the element B and element C precursors.
[176]
When supported three times, a silica carrier is mixed with a molybdenum (Mo) precursor solution, dried, and calcined to prepare a first catalyst, and the first catalyst is mixed with a bismuth (Bi) and iron (Fe) precursor mixed solution and dried , and calcining to prepare a second catalyst, and then mixing, drying, and calcining the second catalyst with a mixed solution of element A and element B precursors to obtain a final catalyst.
[177]
When supported 4 times, a first catalyst is prepared by mixing, drying, and calcining a silica carrier with a molybdenum (Mo) precursor solution, and mixing, drying, and calcining the first catalyst with a bismuth (Bi) precursor solution to form a second catalyst After preparing a catalyst, the second catalyst is mixed with an iron (Fe) precursor solution, dried, and calcined to prepare a third catalyst, and then the third catalyst is mixed with a mixed solution of element A and element B precursor; The final catalyst can be obtained by drying and calcining.
[178]
[179]
Hereinafter, from the manufacturing process of the metal precursor solution, the mixing, drying and sintering processes thereof will be described in detail.
[180]
[181]
Manufacturing process of molybdenum (Mo) precursor solution
[182]
[183]
The step of preparing the molybdenum (Mo) precursor solution may be a step of dissolving the Mo precursor in water at a temperature of 50°C to 80°C.
[184]
It is sufficient that the said temperature range is a temperature enough to melt|dissolve the said Mo precursor.
[185]
As the molybdenum precursor, for example, a nitrate, ammonium salt, or organic complex of molybdenum may be used.
[186]
[187]
In addition, in the step of preparing the molybdenum (Mo) precursor solution, at least one of a water-soluble chelating agent including citric acid, oxalic acid, tartaric acid, hydrogen peroxide, or a combination thereof may be added.
[188]
The additive functions as a strength regulator in the catalyst manufacturing process using the sol-gel method, but in one embodiment serves to make the aqueous solution of the molybdenum (Mo) precursor transparent.
[189]
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. can, but is not limited thereto.
[190]
[191]
Precursor solution manufacturing process other than molybdenum (Mo) precursor solution
[192]
[193]
A precursor solution other than the molybdenum (Mo) precursor solution may vary depending on the desired number of loadings.
[194]
[195]
For example, in order to prepare a mixed solution of the bismuth (Bi), iron (Fe), element A, element B, and element C precursors used in the two-time loading, a small amount of nitric acid, bismuth (Bi), iron (Fe), element A precursor (A = one or more of Ni, Mn, and Co), element B precursor (B = one or more of Zn, Mg, Ca, and Ba), and element C precursor (C = Li) , one or more of Na, K, Rb, and Cs).
[196]
Even in the case of preparing a precursor solution used for loading three or four times, a small amount of nitric acid and a desired metal precursor may be dissolved in water at room temperature.
[197]
As precursors of the elements, nitrates, acetates, chlorides, hydroxides, and the like of each element may be used.
[198]
[199]
The manufacturing process of the molybdenum (Mo) precursor solution and other precursor solutions is independent, and the manufacturing order is not limited.
[200]
However, when preparing each of the precursor solutions, the compounding ratio of the precursors may be controlled so that the molar ratio of the metal satisfies the stoichiometric molar ratio of Chemical Formula 1, specifically, Chemical Formula 1-1.
[201]
[202]
mixing process
[203]
[204]
When the silica carrier or the catalyst of the previous step is mixed with the precursor solution, the mixture may be mixed at 20 ° C. to 30 ° C. for 1 hour to 3 hours, and then further mixed at 70 ° C. to 90 ° C. for 1 hour to 3 hours.
[205]
In such a support process, the precursor solution may be continuously distributed in the pores of the silica carrier or the catalyst in the previous step.
[206]
[207]
drying process
[208]
[209]
The drying of the silica carrier or the mixture of the catalyst and the precursor solution in the previous step may be performed at 90° C. to 130° C. for 10 hours to 15 hours.
[210]
In this drying process, in a state in which the precursor solution is continuously distributed in the pores of the silica carrier or the catalyst of the previous step, the solvent (ie, water) is removed, and only the precursor may remain.
[211]
[212]
firing process
[213]
[214]
The firing process after the drying process may be performed at 180° C. to 300° C. for 1 hour to 6 hours at the time of firing the molybdenum (Mo) precursor, and at 500° C. to 700° C. when firing the metal other than molybdenum (Mo). It can be carried out for 4 to 8 hours. When the temperature of the molybdenum (Mo) precursor is too high, exceeding 300 ℃, all of the precursors may be converted to the MoO 3 phase. It is preferable to increase the temperature during firing.
[215]
In such a calcination process, the precursor mixture is oxidized in a state in which the precursor mixture is continuously distributed in the pores of the silica carrier or the catalyst of the previous step, and can be converted into the metal oxide of Chemical Formula 1 (more specifically, Chemical Formula 1-1). .
[216]
The structure of the catalyst thus formed is as described above.
[217]
[218]
Method for ammoxidation of propylene
[219]
[220]
In another embodiment of the present invention, there is provided a method for ammoxidation of propylene, comprising reacting propylene and ammonia in a reactor in the presence of the catalyst of the embodiment described above.
[221]
The catalyst of one embodiment has high activity and high temperature stability, and may be used for ammoxidation of propylene to increase propylene conversion, acrylonitrile selectivity, and yield.
[222]
[223]
For matters other than the catalyst of the embodiment, reference may be made to matters generally known in the art, and further detailed description thereof will be omitted.
[224]
[225]
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 content of the present invention is not limited by the following examples.
[226]
[227]
Example 1 ((Mo)/(Bi, Fe, Ni, Zn, K)/SiO 2 catalyst)
[228]
(1) Manufacturing process of Mo precursor solution
[229]
30.3 g of a Mo precursor (Ammonium Molybdate) was dissolved in 99 g of water at 80° C., and 15.13 g of citric acid was added thereto to prepare a Mo precursor solution.
[230]
(2) Supporting process of Mo precursor solution in silica carrier (using impregnation method)
[231]
Silica (SiO 2 ) particles having a particle size of 50 μm, a pore diameter of 5.5 nm, a pore volume of 1.2 cm 3 /g according to a nitrogen adsorption method, and a BET specific surface area of ​​688 m 2 /g were used as a carrier.
[232]
49 g of the silica carrier was added to the Mo precursor solution of (1), and stirred at room temperature and 80 ° C. for 1 hour, respectively, so that the Mo precursor solution was sufficiently supported in the pores of the silica carrier.
[233]
(3) Mo/SiO 2 catalyst manufacturing process
[234]
Thereafter, the silica carrier prepared in (2) on which the Mo precursor solution was supported was recovered, dried in an oven at 110 ° C. for 12 hours, and then heat-treated for 6 hours while maintaining a temperature of 200 ° C. in an air atmosphere tubular kiln. , a catalyst in which Mo oxide is supported on a silica carrier (hereinafter, in some cases referred to as "Mo/SiO 2 catalyst") was obtained.
[235]
(4) Bi, Fe, Ni, Zn and K precursor mixture solution manufacturing process
[236]
By dissolving 7.5 g of an Fe precursor (Iron nitrate) and 13.8 g of a Ni precursor (Nickel nitrate) in 48 g of water at room temperature, a mixed solution of Fe and Ni precursor was prepared. Additionally, 5.2 g of Bi precursor (Bismuth nitrate), 1.3 g of Zn precursor (Zinc nitrate), and 0.72 g of K precursor (Potassium nitrate) were added to make a mixed solution, and after the solid precursors were dissolved, an additional 2.4 g of nitric acid was added. , and stirred for at least 30 minutes to form a transparent solution, to obtain a Bi, Fe, Ni, Zn and K precursor mixed solution.
[237]
(5) Supporting process of Bi, Fe, Ni, Zn and K precursor mixed solution in Mo/SiO 2 catalyst (using impregnation method)
[238]
To the Mo / SiO 2 catalyst, the Bi, Fe, Ni, Zn and K precursor mixed solution of (4) was added, and stirred at room temperature and 80 ° C. for 1 hour, respectively, respectively, the Mo / SiO 2 catalyst The Bi, Fe, Ni, Zn and K precursor mixed solution was sufficiently supported in the pores.
[239]
(6) (Mo) / (Bi, Fe, Ni, Zn, K) / SiO 2 catalyst manufacturing process
[240]
Thereafter, the Mo/SiO 2 catalyst prepared in (5) on which the Bi, Fe, Ni, Zn and K precursor mixed solution was supported was recovered, dried in an oven at 110 ° C. for 12 hours, and then in an air atmosphere tubular kiln. The catalyst of Example 1 (hereinafter, in some cases "(Mo) )/(Bi, Fe, Ni, Zn, K)/SiO 2 catalyst”) was obtained.
[241]
(7) Ammoxidation process of propylene
[242]
For activation of the catalyst, 0.2 g of the catalyst of Example 1 was filled in the reactor in which 0.05 g of quartz wool was filled.
[243]
As such, the internal pressure of the reactor filled with the quartz fiber and the catalyst was maintained at normal pressure (1 atm), and while the internal temperature of the reactor was increased at a temperature increase rate of 5 ° C./min, nitrogen and ammonia gas were flowed as a pretreatment process. Accordingly, the internal temperature of the reactor was made to reach 400° C., which is the temperature at which the ammoxidation reaction is possible, so that sufficient pretreatment was performed.
[244]
In this way, air was supplied along with propylene and ammonia as reactants to the reactor in which the pretreatment was completed, and the ammoxidation process of propylene was performed. At this time, the feed amount of the reactant is configured so that the volume ratio of propylene: ammonia: air = 1: 1.0 to 2.0: 1.0 to 4.0, and the total weight hourly space velocity (WHSV) of propylene, ammonia, and air is 1 h It was made to become -1 .　
[245]
After completion of the ammoxidation reaction, the product was recovered and analyzed using various equipment to confirm whether acrylonitrile was well produced.
[246]
The analysis method, analysis result, and the like will be described in detail in the Experimental Examples to be described later.
[247]
[248]
Example 2 ((Mo)/(Bi, Fe, Ni, Zn, K)/SiO 2 catalyst)
[249]
(1) (Mo) / (Bi, Fe, Ni, Zn, K) / SiO 2 catalyst manufacturing process
[250]
A catalyst of Example 2 ((Mo)/(Bi, Fe, Ni, Zn, K)/SiO 2 catalyst) was prepared in the same manner as in Example 1, except that the silica carrier was changed .
[251]
Specifically, in Example 2, a silica carrier having a larger pore diameter and a smaller surface area than in Example 1 was used. More specifically , silica (SiO 2 ) particles having a particle size of 60 μm, a pore diameter of 6.0 nm, a pore volume according to a nitrogen adsorption method of 0.98 cm 3 /g, and a BET specific surface area of ​​645 m 2 /g are supported. was used as
[252]
(2) Ammoxidation process of propylene
[253]
After performing the ammoxidation process of propylene using the catalyst of Example 2 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
[254]
[255]
Example 3 ((Mo)/(Bi, Fe, Ni, Zn, K)/SiO 2 catalyst)
[256]
(1) (Mo) / (Bi, Fe, Ni, Zn, K) / SiO 2 catalyst manufacturing process
[257]
Except for changing the heat treatment temperature of step (6), in the same manner as in Example 1, the catalyst of Example 3 ((Mo)/(Bi, Fe, Ni, Zn and K)/SiO 2 catalyst) was prepared.
[258]
Specifically, in Example 3, the heat treatment temperature was increased by about 30 °C than in Example 1, and the heat treatment was performed at about 610 °C.
[259]
(2) Ammoxidation process of propylene
[260]
After performing the ammoxidation process of propylene using the catalyst of Example 3 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
[261]
[262]
Example 4 ((Mo)/(Bi, Fe)/(Ni, Zn, K)/SiO 2 catalyst)
[263]
(1) (Mo) / (Bi, Fe) / (Ni, Zn, K) / SiO 2 catalyst manufacturing process
[264]
Except that the number of loadings was changed to 3 times (1 time - Mo, 2 times - Bi and Fe, 3 times - Ni, Zn, and K). A catalyst of Example 4 was prepared in the same manner as in Example 1.
[265]
Specifically, 5.2 g of Bi precursor (Bismuth nitrate) and 7.5 g of Fe precursor (Iron nitrate) are dissolved in 60 g of water at room temperature, 15 g of nitric acid is added, and then stirred for 30 minutes or more to form a transparent solution, And Fe precursor mixture solution was prepared.
[266]
Independently, 13.8 g of Ni precursor (Nickel nitrate), 1.3 g of Zn precursor (Zinc nitrate), and 0.72 g of K precursor (Potassium nitrate) were dissolved in 60 g of water at room temperature, 15 g of nitric acid was added, and then a transparent A mixture of Ni, Zn, and K precursors was prepared by stirring for at least 30 minutes to form a solution.
[267]
The Bi and Fe precursor mixed solution was added to the Mo/SiO 2 catalyst prepared in the same manner as in Example 1, and the Bi and Fe precursor solution was supported by sequentially stirring at room temperature and 80 ° C. for 1 hour, respectively, 110 Dry in an oven at ℃ for 12 hours, heat treatment for 6 hours while maintaining a temperature of 580 ℃ in a tubular kiln in an air atmosphere, a catalyst in which Mo oxide and oxides of Bi and Fe are sequentially supported on a silica carrier (hereinafter, in the case Thus, "(Mo)/(Bi, Fe)/SiO 2 catalyst") was obtained.
[268]
Thereafter, the Ni, Zn, and K precursor mixed solution was added to the (Mo)/(Bi and Fe)/SiO 2 catalyst, and the Ni, Zn, and After supporting the K precursor solution, drying in an oven at 110 ° C. for 12 hours, and heat treatment for 6 hours while maintaining a temperature of 580 ° C. in an air atmosphere tubular kiln, Mo oxide on a silica carrier; oxides of Bi and Fe; And Ni, Zn, and the catalyst of Example 4 in which oxides of K are sequentially supported (hereinafter, in some cases, "(Mo)/(Bi, Fe)/(Ni, Zn, K)/SiO 2 catalyst" ) was obtained.
[269]
(2) Ammoxidation process of propylene
[270]
After performing the ammoxidation process of propylene using the catalyst of Example 4 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
[271]
[272]
Example 5 ((Mo)/(Bi)/(Fe, Ni)/(Zn, K)/SiO 2 catalyst)
[273]
(1) (Mo) / (Bi) / (Fe, Ni) / (Zn, K) / SiO 2 catalyst manufacturing process
[274]
The catalyst of Example 5 was prepared in the same manner as in Example 1, except that the number of loadings was changed to 4 times (1 time-Mo, 2 times-Bi, 3 times-Fe and Ni, 4 times-Zn and K) did.
[275]
Specifically, a Bi precursor solution was prepared by dissolving 5.2 g of Bi precursor (Bismuth nitrate) in 60 g of water at room temperature, adding 15 g of nitric acid, and stirring for 30 minutes or more to obtain a transparent solution.
[276]
Independently, 7.5 g of Fe precursor (Iron nitrate) and 13.8 g of Ni precursor (Nickel nitrate) are dissolved in 60 g of water at room temperature, and 15 g of nitric acid is added, followed by stirring for at least 30 minutes to form a transparent solution, A mixed solution of Fe and Ni precursors was prepared.
[277]
Independently, 1.3 g of Zn precursor (Zinc nitrate) and 0.72 g of K precursor (Potassium nitrate) are dissolved in 60 g of water at room temperature, 15 g of nitric acid is added, and then stirred for at least 30 minutes to form a transparent solution Thus, a mixed solution of Zn and K precursors was prepared.
[278]
The Bi precursor solution was added to the Mo/SiO 2 catalyst prepared in the same manner as in Example 1, and the Bi precursor solution was supported by stirring at room temperature and 80° C. for 1 hour, respectively, and then in an oven at 110° C. for 12 hours. The catalyst (hereinafter, in some cases "(Mo)/( Bi)/SiO 2 catalyst”) was obtained.
[279]
Thereafter, the Fe and Ni precursor mixed solution was added to the (Mo) / (Bi) / SiO 2 catalyst, and the Fe and Ni precursor solutions were supported by sequentially stirring at room temperature and 80 ° C. for 1 hour, respectively, Drying in an oven at 110 ° C. for 12 hours, heat treatment for 6 hours while maintaining a temperature of 580 ° C. in an air atmosphere tubular kiln, Mo oxide on a silica carrier; Bi oxide; and a catalyst on which oxides of Fe and Ni were sequentially supported (hereinafter, in some cases, referred to as “(Mo)/(Bi)/(Fe, Ni)/SiO 2 catalyst”) was obtained.
[280]
Then, the (Mo)/(Bi)/(Fe, Ni)/SiO 2 catalyst was supported with the Zn and K precursor mixed solution and then dried and heat treated to form Mo oxide on the silica carrier; Bi oxide; oxides of Fe and Ni; and the catalyst of Example 5 in which oxides of Zn and K are sequentially supported (hereinafter, in some cases, "(Mo)/(Bi)/(Fe, Ni)/(Zn, K)/SiO 2 catalyst" ) was obtained.
[281]
(2) Ammoxidation process of propylene
[282]
After performing the ammoxidation process of propylene using the catalyst of 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.
[283]
[284]
Example 6 ((Mo)/(Bi, Fe, Ni, Zn, K)/SiO 2 catalyst)
[285]
(1) (Mo) / (Bi, Fe, Ni, Zn, K) / SiO 2 catalyst manufacturing process
[286]
A catalyst of Example 6 was prepared in the same manner as in Example 1, except that the amount of Bi precursor, Fe precursor, and Ni precursor was changed. Specifically, 8.7 g of Bi precursor (Bismuth nitrate), 8.7 g of Fe precursor (Iron nitrate), and 13.795 g of Ni precursor (Nickel nitrate) were used.
[287]
(2) Ammoxidation process of propylene
[288]
After performing the ammoxidation process of propylene using the catalyst of Example 6 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
[289]
[290]
Example 7 ((Mo)/(Bi, Fe, Ni, Zn, K)/SiO 2 catalyst)
[291]
(1) (Mo) / (Bi, Fe, Ni, Zn, K) / SiO 2 catalyst manufacturing process
[292]
A catalyst of Example 7 was prepared in the same manner as in Example 1, except that the amount of Bi precursor, Fe precursor, and Ni precursor was changed.
[293]
Specifically, 8.7 g of Bi precursor (Bismuth nitrate), 11.5 g of Fe precursor (Iron nitrate), and 13.8 g of Ni precursor (Nickel nitrate) were used.
[294]
(2) Ammoxidation process of propylene
[295]
After performing the ammoxidation process of propylene using the catalyst of Example 7 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
[296]
[297]
Comparative Example 1 ((Mo, Bi, Fe, Ni, Zn, K)/SiO 2 catalyst)
[298]
(1) (Mo, Bi, Fe, Ni, Zn, K) / SiO 2 catalyst manufacturing process (using sol-gel method)
[299]
First, 16 g of Mo precursor (Ammonium Molybdate) and 1.1 g of Oxalic acid were added to 10 g of distilled water and heated to about 50° C. to prepare a Mo precursor solution.
[300]
Independently, in 5 g of water at room temperature, Bi precursor (Bismuth nitrate) 1.73 g, Fe precursor (Iron nitrate) 2.01 g, Ni precursor (Nickel nitrate) 0.6533 g, Zn precursor (Zinc nitrate) 0.3159 g, K precursor ( Potassium nitrate) 0.2148 g was dissolved to prepare a Bi, Fe, Ni, Zn, and K precursor mixed solution.
[301]
the Mo precursor solution; and the Bi, Fe, Ni, Zn, and K precursor mixture solution was mixed with stirring, and then 42.4 g of silica sol (LUDOX AS 40, content: 40 %, Grace) was added thereto and stirred, followed by a rotating disk type. Spray drying was performed at 120 °C (inlet) and 230 °C (outlet) conditions using a spray dryer (device name: BUCHI mini spray dryer).
[302]
The powder thus obtained was calcined at 580° C. for 3 hours to finally obtain the catalyst of Comparative Example 1.
[303]
(2) Ammoxidation process of propylene
[304]
The catalyst of Comparative Example 1 was used instead of the catalyst of Example 1, and the ammoxidation process of propylene was performed in the same manner as in Example 1.
[305]
After completion of the ammoxidation reaction of Comparative Example 1, the product was recovered and analyzed in the same manner as in Example 1.
[306]
[307]
Comparative Example 2 ((Mo, Bi, Fe, Ni, Zn, K)/SiO 2 catalyst)
[308]
(1) (Mo, Bi, Fe, Ni, Zn, K) / SiO 2 catalyst manufacturing process (using sol-gel method)
[309]
A catalyst of Comparative Example 2 was prepared in the same manner as in Comparative Example 1, except that the amount of silica sol, Bi precursor, Fe precursor, Zn precursor, and K precursor was changed.
[310]
Specifically, silica sol (LUDOX AS 40, solid content: 40 %, Grace) 34 g, Bi precursor (Bismuth nitrate) 2.1 g, Fe precursor (Iron nitrate) 3.7 g, Zn precursor (Zinc nitrate) 0.63 g, K precursor (Potassium nitrate) 0.36 g was used.
[311]
(2) Ammoxidation process of propylene
[312]
After performing the ammoxidation process of propylene using the catalyst of Comparative Example 2 instead of the catalyst of Comparative Example 1, the product was recovered, and analysis was performed in the same manner as in Comparative Example 1.
[313]
[314]
Comparative Example 3 ((Mo)/(Bi, Ce, Fe, Mg, Rb)/SiO 2 catalyst)
[315]
(1) (Mo)/(Bi, Ce, Fe, Mg, Rb)/SiO 2 catalyst manufacturing process (using impregnation method)
[316]
Comparative Example 3 in the same manner as in Example 1, except that the amount of the Mo precursor was changed, and a Bi, Ce, Fe, Mg, and Rb precursor mixed solution was used instead of the Bi, Fe, Ni, Zn, and K precursor mixed solution. of the catalyst was prepared.
[317]
Specifically, when preparing the Mo precursor solution, 18.241 g of the Mo precursor (Molybdenum nitrate) was used. In addition, when preparing a mixed solution of Bi, Ce, Fe, Mg and Rb precursors, Bi precursor (Bismuth nitrate) 3.449 g, Ce precursor (Cerium nitrate) 0.580 g, Fe precursor (Iron nitrate) 13.646 g, Mg precursor (Magnesium nitrate) 14.92 g and 0.426 g of Rb precursor (Rubidum nitrate) were used.
[318]
(2) Ammoxidation process of propylene
[319]
After performing the ammoxidation process of propylene using the catalyst of Comparative Example 3 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
[320]
[321]
Comparative Example 4 ((Mo)/(Bi, Fe, Ni, Zn, Mn, La, Pr, K, Cs)/SiO 2 catalyst)
[322]
(1) (Mo)/(Bi, Fe, Ni, Zn, Mn, La, Pr, K, Cs)/SiO 2 catalyst manufacturing process (using impregnation method)
[323]
Except for changing the amount of the Mo precursor and using the Bi, Fe, Ni, Zn, Mn, La, Pr, K, and Cs precursor mixed solution instead of the Bi, Fe, Ni, Zn, and K metal precursor mixed solution, A catalyst of Comparative Example 4 was prepared in the same manner as in Example 1.
[324]
Specifically, when preparing the Mo precursor solution, 18.241 g of the Mo precursor (Molybdenum nitrate) was used. In addition, when preparing a mixed solution of Bi, Fe, Ni, Zn, Mn, La, Pr, K, and Cs precursor, Bi precursor (Bismuth nitrate) 5.66 g, Fe precursor (Iron nitrate) 8.8 g, Ni precursor (Nickel nitrate) 24.01 g, Zn precursor (Zinc nitrate) 4.95 g, Mn precursor (manganese nitrate) 2.4 g, La precursor (Lantanum nitrate) 1.44 g, Pr precursor (Praseodymium nitrate), K precursor (Potassium nitrate) 0.674 g, and Cs precursor (Cesium) nitrate) 0.325 g was used.
[325]
(2) Ammoxidation process of propylene
[326]
After performing the ammoxidation process of propylene using the catalyst of Comparative Example 4 instead of the catalyst of Example 1, the product was recovered, and analysis was performed in the same manner as in Example 1.
[327]
[328]
Comparative Example 5 ((Mo, Bi)/SiO 2 catalyst)
[329]
(1) (Mo, Bi) / SiO 2 catalyst manufacturing process (using impregnation method)
[330]
A catalyst of Comparative Example 5 was prepared in the same manner as in Example 1, except that the amount of the Mo precursor was changed and a Bi precursor solution was used instead of the Bi, Fe, Ni, Zn, and K precursor mixed solution.
[331]
Specifically, when preparing the Mo precursor solution, 3 g of the Mo precursor (Molybdenum nitrate) was used. In addition, when preparing the Bi precursor solution, 16 g of Bi precursor (Bismuth nitrate) was used.
[332]
(2) Ammoxidation process of propylene
[333]
After performing the ammoxidation process of propylene 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.
[334]
[335]
Experimental Example 1: Catalyst Analysis
[336]
[337]
Each catalyst of Examples and Comparative Examples was analyzed according to the following analysis method, and the analysis results are shown in Table 1 below. For reference, each metal oxide composition of Examples and Comparative Examples and the mixing ratio with the carrier are also shown in Table 1 below:
[338]
[339]
BET specific surface area : BET specific surface area for each catalyst of Examples and Comparative Examples was measured using a BET specific surface area measuring instrument (manufacturer: BEL Japan, instrument name: BELSORP_Mini).
[340]
Specifically, in the device, the adsorption amount up to the relative pressure (P/P0) 1 was measured under the liquid nitrogen temperature (77 K), and the desorption amount up to the relative pressure (P/P0) 0.03 was also measured. These measurements were applied to the BJH equation to determine the pore volume, diameter, and surface area of ​​the catalyst.
[341]
[342]
Ammonia adsorption amount : Ammonia adsorption amount for each catalyst of Examples and Comparative Examples was measured using a device capable of measuring by ammonia temperature elevation desorption method (NH 3 -TPD) (manufacturer: Micromeritics, device name: Autochem II 2920). .
[343]
Specifically, the U-shaped quartz tube in the device is filled with about 0.1 g of catalyst, the U-shaped reactor is connected to the device, and then the temperature is raised from room temperature at a temperature increase rate of 10 °C/min using helium gas (50 cc/min). After raising the temperature to about 400 °C, the pretreatment was performed while maintaining the temperature at 400 °C for about 1 hour. This is to remove organic matter remaining in the catalyst.
[344]
After the pretreatment is completed, NH 3 is adsorbed for 1 hour at about 100° C. with 10% NH 3 /He (50 cc/min) . While flowing He at the same temperature, the physically adsorbed NH 3 was removed, and the desorbed NH 3 was measured while the temperature was raised to 800 °C .
[345]
Thereafter, by obtaining the difference between the initial adsorption amount (a) and the desorption amount (b) of NH 3 , the adsorption amount of NH 3 remaining on the catalyst surface could be obtained.
[346]
[347]
[Table 1]
quite number of loadings Catalyst Analysis Results
Metal oxide composition and
mixing ratio with carrier Pore ​​Diameter (nm) BET specific surface area
(m 2 /g) Ammonia adsorption
(mmol/g)
Example 1 impregnation Twice
(Mo - Bi, Fe, Ni, Zn, K) Mo 12 Bi 0.75 Fe 1.3 Ni 2.5 Zn 0.3 K 0.5 O y : 25wt%,
SiO2 : 75wt % 8.1 217.8 0.72
Example 2 impregnation Twice (Mo - Bi, Fe, Ni, Zn, K) Mo 12 Bi 0.7 5Fe 1.3 Ni 2.5 Zn 0.3 K 0.5 O y : 25wt%, SiO 2 : 75wt% 8.5 210.2 0.69
Example 3 impregnation Twice (Mo - Bi, Fe, Ni, Zn, K) Mo 12 Bi 0.75 Fe 1.3 Ni 2.5 Zn 0.3 K 0.5 O y : 25wt%,
SiO2 : 75wt % 8.6 196.5 0.63
Example 4 impregnation 3 times (Mo - Bi, Fe - Ni, Zn, K) Mo 12 Bi 0.75 Fe 1.3 Ni 2.5 Zn 0.3 K 0.5 O y : 25wt%,
SiO2 : 75wt % 7.9 225.2 0.68
Example 5 impregnation 4 times (Mo - Bi - Ni, Fe - Zn, K) Mo 12 Bi 0.75 Fe 1.3 Ni 2.5 Zn 0.3 K 0.5 O y : 25wt%, SiO2 : 75wt % 9.2 178.5 0.59
Example 6 impregnation Twice (Mo - Bi, Fe, Ni, Zn, K) Mo 12 Bi 1.25 Fe 1.5 Ni 3.5 Zn 0.3 K 0.5 O y : 25wt%, SiO2 : 75wt % 8.4 213.1 0.66
Example 7 impregnation Twice (Mo - Bi, Fe, Ni, Zn, K) Mo 12 Bi 1.25 Fe 2.0 Ni 4.0 Zn 0.3 K 0.5 O y : 25wt%, SiO2 : 75wt % 8.4 212.5 0.67
Comparative Example 1 sol-gel method Once (Mo, Bi, Fe, Ni, Zn, K) Mo 12 Bi 0.5 Fe 0.7 Ni 0.5 Zn 0.15 K 0.3 O y : 50wt%, SiO 2 : 50wt% 13.6 35.8 0.14
Comparative Example 2 sol-gel method Once (Mo, Bi, Fe, Ni, Zn, K) Mo 12 Bi 0.6 Fe 1.3 Ni 0.5 Zn 0.3 K 0.5 O y : 50wt%,
SiO2 : 50wt % 13.8 34.6 0.14
Comparative Example 3 impregnation Twice (Mo - Bi, Ce, Fe, Mg, Rb) Mo 12.4 Bi 0.32 Ce 0.08 Fe 1.52 Ni 6.51 Mg 2.62 Rb 0.13 : 25wt%, SiO 2 : 75wt% 8.2 231.8 0.40
Comparative Example 4 impregnation Twice (Mo - Bi, Fe, Ni, Zn, Mn, La, Pr, K, Cs) Mo 12 Bi 0.7 Fe 1.3 Ni 5.5 Zn 1 Mn 0.5 La 0.2 Pr 0.02 K 0.4 Cs 0.1 O x : 25wt%,
SiO 2 : 75wt% 8.4 225.3 0.41
Comparative Example 5 impregnation Twice (Mo-Bi) Bi 2 O 3 MoO 3 : 25wt%, SiO 2 : 75wt% 8.1 226.4 0.22
[348]
Experimental Example 2: Analysis of ammoxidation products of propylene
[349]
[350]
Each ammoxidation product of Examples and Comparative Examples was analyzed using chromatography (Gas chromatography, manufacturer: Agilent machine name: HP 6890 N) equipped with FID (Flame Ionization Detector and TCD (Thermal Conductivity Detector)).
[351]
Specifically, products such as ethylene (ehthlene), hydrogen cyanide, acetaldehyde, acetonitrile, acroleing, and acrylonitrile were analyzed by FID, and TCD was analyzed. Gas products such as NH 3 , O 2 , CO and CO 2 and unreacted propylene were analyzed to determine the number of moles of propylene reacted in Examples and Comparative Examples and the number of moles of ammoxidation products, respectively.
[352]
By substituting the number of moles of propylene supplied along with the analysis result according to the following 1, 2, and 3, the conversion rate of propylene, the selectivity and yield of acrylonitrile, which is an ammoxidation product of propylene, are calculated, and the calculated values ​​are Table 2 shows.
[353]
[Equation 1]
[354]
Conversion of propylene (%)
[355]
=100*(number of moles of ammoxidation of reacted propylene)/(number of moles of propylene supplied)
[356]
[Equation 2]
[357]
Selectivity of acrylonitrile (%)
[358]
=100*(number of moles of acrylonitrile produced)/(number of moles of reacted propylene)
[359]
[Equation 3]
[360]
Yield of acrylonitrile (%)
[361]
=100*(number of moles of acrylonitrile produced)/(number of moles of propylene supplied)
[362]
[363]
In addition, the Mo loss rate was measured after the reaction of Examples and Comparative Examples by the following method, and the measurement results are shown in Table 2 below.
[364]
[365]
[Table 2]
Ammoxidation products of propylene
Propylene conversion
(%) Acrylonitrile Selectivity
(%) Acrylonitrile Yield
(%) Mo reduction rate
(%)
Example 1 87.7 75.6 66.4 0
Example 2 85.9 76.7 65.9 0
Example 3 87.4 75.9 66.3 0
Example 4 87.2 74.4 64.9 0
Example 5 76.8 77.3 59.4 0
Example 6 80.6 78.4 63.2 0
Example 7 79.5 78.6 62.5 0
Comparative Example 1 68.3 73.3 50.5 4.2
Comparative Example 2 64.2 75.8 48.6 4.0
Comparative Example 3 74.3 69.5 51.6 0
Comparative Example 4 15.2 62.4 9.5 0
Comparative Example 5 12.5 58 7.3 10.3
[366]
evaluation
[367]
[368]
In Table 2, in the catalysts of Examples 1 to 7, the conversion rate of propylene and the yield of acrylonitrile were significantly higher than the catalysts of Comparative Examples 1 to 5, and the loss of Mo during the ammoxidation reaction of propylene did not occur at all. can confirm that it is not.
[369]
[370]
Specifically, looking at Tables 1 and 2 above, the catalysts of Examples 1 to 7 prepared by the impregnation method adsorbed a large amount of ammonia compared to the catalysts of Comparative Examples 1 to 3 prepared by the sol-gel method. , it can be seen that it contributed to increasing the conversion rate of propylene and the yield of acrylonitrile according to the ammoxidation reaction of propylene.
[371]
In particular, the catalysts of Examples 1 to 7 are prepared by controlling the number of times of supporting the metal oxide to two or more even in the impregnation method, so that the molybdenum (Mo) oxide is supported first, and the metal oxide of a different type is It can be seen that the elution of molybdenum (Mo) is suppressed during the ammoxidation reaction of propylene as it has a supported structure later.
[372]
[373]
However, although the catalysts of Comparative Examples 3 to 5 were prepared by controlling the number of times of supporting the metal oxide to two or more, the conversion rate of propylene and the yield of acrylonitrile were significantly lower compared to Examples 1 to 7.
[374]
Specifically, Comparative Example 3 including Ce and the like as the active metal; And in the case of Comparative Example 4 containing La, Pr, and the like, the conversion rate of propylene and the yield of acrylonitrile are reduced under the influence of the active metal.
[375]
In particular, in Comparative Example 5 containing only Mo and Bi as active metals, the conversion rate of propylene and the yield of acrylonitrile were significantly lowered, and it seemed that it was difficult to suppress the elution of Mo with Bi alone.
[376]
[377]
Therefore, with reference to Examples, the catalyst stability is increased by controlling the number of times of supporting the metal oxide, the overall composition of the metal oxide, etc. within the scope of the above-described embodiment, and the conversion rate of propylene, the selectivity of acrylonitrile and the yield are desired. range can be adjusted.
Claims
[Claim 1]
silica carrier; and a catalyst for ammoxidation of propylene comprising a metal oxide supported on the silica carrier, wherein the metal oxide has an overall composition satisfying the following Chemical Formula 1, a coating layer comprising molybdenum (Mo) oxide; and one or more coating layers positioned on the coating layer containing the molybdenum (Mo) oxide, and including a dissimilar metal. [Formula 1] Mo 12 Bi a Fe b A c B d C e D F O x In Formula 1, A is one or more of Ni, Mn, and Co, and B is Zn, Mg, Ca, and Ba At least one element, C is at least one of Li, Na, K, Rb, and Cs, D is at least one of Cr, W, B, Al, Ca, and V, wherein a to f, and x is the fraction of an atom or group, respectively, a is 0.1 to 5, b is 0.1 to 5, c is 0.01 to 10, d is 0.01 to 10, e is 0.01 to 2, and f is 0 to 10; , x is 24-48.
[Claim 2]
According to claim 1, wherein the metal oxide, the overall composition of which satisfies the following Chemical Formula 1, a first coating layer comprising molybdenum (Mo) oxide; and bismuth (Bi), iron (Fe), element A (A = at least one of Ni, Mn, and Co), element B (B = among Zn, Mg, Ca, and Ba), located on the first coating layer. at least one element), and a second coating layer comprising an oxide of element C (at least one of C=Li, Na, K, Rb, and Cs); or a second coating layer comprising molybdenum (Mo) oxide 1 coating layer; and a second coating layer disposed on the first coating layer and including oxides of bismuth (Bi) and iron (Fe); and Element A (A=at least one of Ni, Mn, and Co), Element B (B=at least one of Zn, Mg, Ca, and Ba), and Element C (C) located on the second coating layer = a third coating layer comprising an oxide of Li, Na, K, Rb, and Cs); or a first coating layer comprising molybdenum (Mo) oxide; and a second coating layer disposed on the first coating layer and including bismuth (Bi) oxide. a third coating layer positioned on the second coating layer and including iron (Fe) oxide; and Element A (A=at least one of Ni, Mn, and Co), Element B (B=at least one of Zn, Mg, Ca, and Ba), and Element C (C) located on the third coating layer = Li, Na, K, Rb, and a fourth coating layer comprising an oxide of (one or more elements of Cs); which, comprising, a catalyst for ammoxidation of propylene.
[Claim 3]
The catalyst for ammoxidation of propylene according to claim 1, wherein the metals of the adjacent coating layers are chemically bonded to each other.
[Claim 4]
The method according to claim 1, wherein the catalyst comprises: a silica carrier including second pores; an inner coating layer continuously coating the wall surfaces of the second pores and including the metal oxide; and a first pore located inside the second pore and occupying an empty space excluding the inner coating layer.
[Claim 5]
The catalyst for ammoxidation of propylene according to claim 1, wherein the metal oxide has an overall composition that satisfies the following Chemical Formula 1-1: [Formula 1-1] Mo 12 Bi a Fe b Ni c Zn d K e O x In Formula 1-1, each definition of a to e, and x is the same as in claim 1.
[Claim 6]
The catalyst for ammoxidation of propylene according to claim 1, wherein the weight ratio of the metal oxide and the silica carrier is 15:85 to 35:65.
[Claim 7]
The catalyst for ammoxidation of propylene according to claim 1, wherein the silica carrier includes pores having a diameter of 4 nm to 40 nm.
[Claim 8]
The catalyst for ammoxidation of propylene according to claim 1, wherein the catalyst has a D50 particle diameter of 50 μm to 150 μm.
[Claim 9]
The catalyst for ammoxidation of propylene according to claim 1, wherein the catalyst includes pores having a diameter of 4 nm to 40 nm.
[Claim 10]
The catalyst for ammoxidation of propylene according to claim 1, wherein the catalyst has a BET specific surface area of ​​100 m 2 /g to 300 m 2 /g.
[Claim 11]
The catalyst for ammoxidation of propylene according to claim 1, wherein the catalyst has an ammonia adsorption amount of 0.5 mmol/g to 5 mmol/g measured by ammonia temperature elevated desorption method (NH 3 -TPD).
[Claim 12]
preparing a first catalyst by supporting molybdenum (Mo) oxide on a silica carrier; and supporting an oxide of a heterogeneous metal on the first catalyst to obtain a catalyst in which a metal oxide satisfying the following Chemical Formula 1 is supported on a silica carrier; A catalyst for ammoxidation of propylene comprising a As a manufacturing method, the metal oxide, a coating layer comprising molybdenum (Mo) oxide; And located on the coating layer containing the molybdenum (Mo) oxide, and at least one coating layer containing a dissimilar metal; Method for producing a catalyst for ammoxidation of propylene, comprising: [Formula 1] Mo 12 Bi a Fe b A c B d C e D F O xIn Formula 1, A is at least one of Ni, Mn, and Co, B is at least one of Zn, Mg, Ca, and Ba, and C is at least one of Li, Na, K, Rb, and Cs. element, D is one or more of Cr, W, B, Al, Ca, and V, wherein a to f and x are each an atom or fraction of an atomic group, a is 0.1 to 5, and b is 0.1 to 5, c is from 0.01 to 10, d is from 0.01 to 10, e is from 0.01 to 2, f is from 0 to 10, and x is from 24 to 48.
[Claim 13]
13. The method of claim 12, wherein the step of supporting the oxide of the heterogeneous metal on the first catalyst comprises bismuth (Bi), iron (Fe), element A (A = Ni, Mn, and Co) on the first catalyst. one or more of elements), element B (B = one or more elements of Zn, Mg, Ca, and Ba, and element C (C = one or more elements of Li, Na, K, Rb, and Cs). or oxides of bismuth (Bi) and iron (Fe) in the first catalyst, element A (A = at least one of Ni, Mn, and Co), element B (B = Zn, Mg, Ca) , and at least one element of Ba), and sequentially supporting an oxide of element C (C = at least one element of Li, Na, K, Rb, and Cs); containing, or bismuth ( Bi) oxide; iron (Fe) oxide; and element A (A = one or more of Ni, Mn, and Co), element B (B = one or more of Zn, Mg, Ca, and Ba), and element C (C = Li, Na, K, Rb, and the step of sequentially supporting the oxide of one or more elements of Cs); will, comprising a method for producing a catalyst for ammoxidation of propylene.
[Claim 14]
The method of claim 12, wherein preparing the first catalyst comprises: preparing a molybdenum (Mo) precursor solution; mixing the silica carrier and the molybdenum (Mo) precursor solution; drying the silica carrier on which the molybdenum (Mo) precursor solution is supported to obtain a silica carrier on which the molybdenum (Mo) precursor is supported; and calcining the silica carrier on which the molybdenum (Mo) precursor is supported.
[Claim 15]
15. The method of claim 14, wherein the drying is carried out at 90 °C to 130 °C for 10 to 15 hours, and the calcination is performed at 180 °C to 300 °C for 1 hour to 6 hours, the method for producing a catalyst for ammoxidation of propylene .
[Claim 16]
The method of claim 12, wherein the supporting of the oxide of the dissimilar metal on the first catalyst comprises: preparing a precursor solution of the dissimilar metal; mixing a precursor solution of a dissimilar metal and a first catalyst; drying the mixture at 90° C. to 130° C. for 10 to 15 hours; and calcining at 500° C. to 700° C. for 4 hours to 7 hours.
[Claim 17]
A process for the ammoxidation of propylene comprising reacting propylene and ammonia in a reactor in the presence of the catalyst of claim 1 .