Catalyst for ammoxidation reaction, method for producing catalyst for ammoxidation reaction, and ammonia oxidation method

Abstract

Provided are a catalyst for an ammoxidation reaction, a method for producing the catalyst for an ammoxidation reaction, and a method for ammoxidation.

Description

Catalyst for ammoxidation reaction, method for producing catalyst for ammoxidation reaction, and ammoxidation method

[0001] It relates to a catalyst for ammoxidation reaction, a method for producing a catalyst for ammoxidation reaction, and an ammoxidation method.

[0002]

[0003] Acrylonitrile production was previously accomplished through the reaction of HCN (hydrogen cyanide) and acetylene. Commercial production is now underway utilizing the reaction of propylene, ammonia, and air. This process involves the ammoxidation of propylene to produce acrylonitrile. A wide variety of catalysts have been reported for this reaction. Specifically, molybdenum (Mo) is used as a base, along with a mixture of up to eight elements, including transition metals, precious metals, and alkali metals. However, the use of bismuth (Bi) has been reported to increase acrylonitrile selectivity.

[0004] Conventional catalyst synthesis methods used in this ammoxidation reaction utilize nitric acid, which can be toxic to humans and the environment. Therefore, a method for producing a catalyst that combines various elements without using nitric acid, while also increasing acrylonitrile selectivity, would be desirable.

[0005] [Previous literature]

[0006] [Patent Document]

[0007] Republic of Korea Patent Registration No. 10-0681222

[0008]

[0009] The present invention provides a catalyst for ammoxidation that increases the selectivity of acrylonitrile in the production of acrylonitrile by ammoxidation and reduces the selectivity of side reactions that cause problems in the process during ammoxidation.

[0010] The present invention provides a method for manufacturing a catalyst for ammoxidation reaction that is friendly to humans and the environment by not using nitric acid in the manufacturing of the catalyst for ammoxidation reaction.

[0011]

[0012] One aspect provides a catalyst for ammoxidation reaction for the production of acrylonitrile.

[0013] 1. The catalyst for the above ammoxidation reaction comprises a complex oxide, and the complex oxide is represented by the following chemical formula 1:

[0014] [Chemical Formula 1]

[0015] Mo1Bi a Fe b Co c Ni d O e

[0016] (In Chemical Formula 1, a, b, c, d, e, and f are each the molar ratio of each element relative to 1 mole of molybdenum, a is 0.05 or more and 0.20 or less, b is 0.05 or more and less than 0.15, c is 0 or more and 0.25 or less, d is 0.52 or more and 0.75 or less, and e is the number of oxygen atoms required to satisfy the valence of other elements present.)

[0017] In 2.1, the ratio of the molar ratio of nickel to the molar ratio of cobalt in the above chemical formula 1 may be 4 to 8.

[0018] In 3.1-2, the ratio of the molar ratio of bismuth to the molar ratio of iron in the chemical formula 1 may be 1 to 5.

[0019] In 4.1-3, the catalyst for the ammoxidation reaction further includes a carrier, and the carrier may include silica.

[0020] In 5.1-4, the catalyst for the ammoxidation reaction may include the composite oxide: carrier in an amount of 50 to 90 wt%: 10 to 50 wt% among the total of 100 wt% of the composite oxide and the carrier.

[0021] Another aspect provides a method for preparing a catalyst for ammoxidation for the production of acrylonitrile.

[0022] 6. A method for producing a catalyst for ammoxidation reaction for producing acrylonitrile,

[0023] A method comprising the steps of preparing a mixture of catalyst precursors such that the molar ratio of metals satisfies the stoichiometric molar ratio of the following chemical formula 1, pulverizing the mixture of catalyst precursors, drying the pulverized mixture, and calcining the dried mixture to prepare a composite oxide of the following chemical formula 1, wherein the preparation method does not use nitric acid:

[0024] [Chemical Formula 1]

[0025] Mo1Bi a Fe b Co c Ni d O e

[0026] (In Chemical Formula 1, a, b, c, d, e, and f are each the molar ratio of each element relative to 1 mole of molybdenum, a is 0.05 or more and 0.20 or less, b is 0.05 or more and less than 0.15, c is 0 or more and 0.25 or less, d is 0.52 or more and 0.75 or less, and e is the number of oxygen atoms required to satisfy the valence of other elements present.)

[0027] In 7.6, the crushing can be performed by ball milling.

[0028] In 8.6-7, the ball milling can be performed at a milling speed of 10 to 30 Hz, a milling temperature of 20 to 50°C, and a milling time of 10 to 60 minutes.

[0029] In 9.6-8, the grinding may be performed in a state in which at least one of water and alcohol is additionally included in the mixture of the catalyst precursor.

[0030] Another aspect provides a method for preparing a catalyst for ammoxidation reaction for the production of acrylonitrile.

[0031] The above manufacturing method comprises a step of reacting propylene and ammonia in the presence of the catalyst.

[0032]

[0033] A catalyst for ammoxidation is provided that increases the selectivity of acrylonitrile in the production of acrylonitrile by ammoxidation and reduces the selectivity of side reactions that cause problems in the process during ammoxidation.

[0034] A method for manufacturing a catalyst for ammoxidation reaction that is friendly to humans and the environment is provided because nitric acid is not used in the manufacturing of the catalyst for ammoxidation reaction.

[0035]

[0036] Figure 1 illustrates a series of practical steps for manufacturing the catalyst of the present invention.

[0037]

[0038] The above objectives, other objectives, features, and advantages will be readily understood through the following preferred embodiments, illustrated in the accompanying drawings. However, the embodiments described herein are not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete, and to sufficiently convey the technical concepts to those skilled in the art.

[0039] Singular expressions include plural expressions unless the context clearly indicates otherwise.

[0040] In this specification, terms such as “include” or “have” are intended to specify the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but should be understood not to exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0041] Unless otherwise specified, all numbers, values, and / or expressions expressing quantities of ingredients, reaction conditions, polymer compositions, and blends used herein are approximations that inherently reflect, among other things, the various uncertainties of measurement that arise in obtaining such values, and therefore should be understood as being modified in all instances by the term "about." Furthermore, whenever a numerical range is disclosed herein, such range is continuous and includes every value from the minimum value to the maximum value inclusive, unless otherwise indicated. Furthermore, whenever such a range refers to integers, every integer from the minimum value to the maximum value inclusive, unless otherwise indicated, is included.

[0042] In this specification, when a range is described for a variable, the variable will be understood to include all values ​​within the described range including the described endpoints of the range. For example, the range "5 to 10" will be understood to include the values ​​5, 6, 7, 8, 9, and 10, as well as any subranges such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc., and any value between integers that fall within the described range, such as 5.5, 6.5, 7.5, 5.5 to 8.5, and 6.5 to 9. Also, for example, a range of "10% to 30%" would be understood to include all integers up to and including 30%, as well as any subranges such as 10% to 15%, 12% to 18%, 20% to 30%, etc., and any value between reasonable integers within the stated range, such as 10.5%, 15.5%, 25.5%, etc.

[0043] Hereinafter, a catalyst for ammoxidation reaction according to an embodiment is described.

[0044] Catalyst for ammoxidation reaction

[0045] The above ammoxidation catalyst catalyzes the ammoxidation of propylene, thereby enabling the production of acrylonitrile from propylene.

[0046] The catalyst for the above ammoxidation reaction comprises a complex oxide, and the complex oxide is represented by the following chemical formula 1:

[0047] [Chemical Formula 1]

[0048] Mo1Bi a Fe b Co c Ni d O e

[0049] (In Chemical Formula 1, a, b, c, d, e, and f are each the molar ratio of each element relative to 1 mole of molybdenum, a is 0.05 or more and 0.20 or less, b is 0.05 or more and less than 0.15, c is 0 or more and 0.25 or less, d is 0.52 or more and 0.75 or less, and e is the number of oxygen atoms required to satisfy the valence of other elements present.)

[0050] Among the above catalysts for ammoxidation, the composite oxide contains molybdenum, bismuth, iron, cobalt, and nickel as metal elements, and does not contain any elements other than the metal elements described above. That is, the catalyst for ammoxidation contains only molybdenum, bismuth, iron, cobalt, and nickel as metal elements, and the sum of molybdenum, bismuth, iron, cobalt, and nickel among all metal elements contained in the catalyst is 100 mol%.

[0051] The above bismuth is contained in a molar ratio of 0.05 or more and 0.20 or less with respect to molybdenum. When the above bismuth is contained in a molar ratio of 0.05 or more, the ammoxidation reaction of propylene can be catalyzed, thereby increasing the selectivity and yield of acrylonitrile. When the above bismuth is contained in a molar ratio of 0.20 or less, the ammoxidation reaction of propylene can be catalyzed, thereby increasing the selectivity and yield of acrylonitrile.

[0052] For example, the bismuth may be contained in a molar ratio of 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, or 0.05 to 0.19 per 1 mole of molybdenum.

[0053] The iron is contained in a molar ratio of 0.05 or more and less than 0.15 with respect to molybdenum. When the iron is contained in a molar ratio of 0.05 or more, the ammoxidation reaction of propylene can be catalyzed, thereby increasing the selectivity and yield of acrylonitrile. When the iron is contained in a molar ratio of less than 0.15, the ammoxidation reaction of propylene can be catalyzed, thereby increasing the selectivity and yield of acrylonitrile.

[0054] For example, the iron may be contained in a molar ratio of 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, for example, 0.05 to 0.09, with respect to 1 mole of molybdenum.

[0055] The above cobalt is contained in a molar ratio of 0 or more and 0.25 or less with respect to molybdenum. When the above cobalt is contained in a molar ratio of 0 or more, the ammoxidation reaction of propylene can be catalyzed, thereby increasing the selectivity and yield of acrylonitrile. When the above cobalt is contained in a molar ratio of 0.25 or less, the ammoxidation reaction of propylene can be catalyzed, thereby increasing the selectivity and yield of acrylonitrile.

[0056] For example, the cobalt may be contained in a molar ratio of 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.05 to 0.15 per 1 mole of molybdenum.

[0057] The nickel is contained in a molar ratio of 0.52 or more and 0.75 or less with respect to molybdenum. When the nickel is contained in a molar ratio of 0.52 or more, the ammoxidation reaction of propylene can be catalyzed, thereby increasing the selectivity and yield of acrylonitrile. When the nickel is contained in a molar ratio of 0.75 or less, the ammoxidation reaction of propylene can be catalyzed, thereby increasing the selectivity and yield of acrylonitrile.

[0058] For example, the nickel may be contained in a molar ratio of 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.52 to 0.7 per 1 mole of molybdenum.

[0059] In the above chemical formula 1, e is the number of oxygen atoms required to satisfy the valence of other elements, for example, 1 to 50, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,48, 49, 50, 1 to 20, 1 to 10. It can be. In the above ammoxidation reaction catalyst, e in chemical formula 1 can be obtained using Rietveld method analysis data.

[0060] In one specific example, when looking at the molar ratio of cobalt to the molar ratio of nickel per mole of molybdenum in the catalyst, the ratio (d / c) of the molar ratio of nickel to the molar ratio of cobalt may be 4 to 8, for example, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, for example, 5 to 7, 5 to 6.5. Within the above range, it may be possible to manufacture a catalyst comprising molybdenum, bismuth, iron, cobalt, and nickel, which increases the selectivity and yield of acrylonitrile.

[0061] In one specific example, when looking at the molar ratio of bismuth to the molar ratio of iron per mole of molybdenum in the catalyst, the ratio (a / b) of the molar ratio of bismuth to the molar ratio of iron may be 1 to 5, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, for example, 1 to 4. In the above range, it may be possible to manufacture a catalyst comprising molybdenum, bismuth, iron, cobalt, and nickel, which increases the selectivity and yield of acrylonitrile.

[0062] In one specific example, in the catalyst, a + b + c + d may be less than 1, for example, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 0.99, for example, 0.5 or more and less than 1, for example, 0.5 to 0.99, 0.7 to 0.99. In the above range, it may be possible to manufacture a catalyst comprising molybdenum, bismuth, iron, cobalt, and nickel, which increases the selectivity and yield of acrylonitrile.

[0063] In one specific example, in the catalyst, a + b may be less than 1, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, for example, 0.1 or more and less than 1, for example, 0.1 to 0.5, 0.1 to 0.3. In the above range, it may be possible to manufacture a catalyst comprising molybdenum, bismuth, iron, cobalt, and nickel, which increases the selectivity and yield of acrylonitrile.

[0064] In one specific example, in the catalyst, c + d may be less than 1, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, for example, 0.1 or more and less than 1, for example, 0.5 to 0.9, 0.5 to 0.8. In the above range, it may be possible to manufacture a catalyst comprising molybdenum, bismuth, iron, cobalt, and nickel, which increases the selectivity and yield of acrylonitrile.

[0065] The above catalyst for ammoxidation reaction may further contain silica.

[0066] The silica may be used as a carrier on which a composite oxide is supported in the ammoxidation catalyst. For example, in the ammoxidation catalyst, the composite oxide and the carrier may be included in a weight ratio of 50 to 90 wt%: 10 to 50 wt%, out of a total of 100 wt% of the composite oxide and the carrier. For example, the weight ratio may be 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, or 90:10. Within the above range, the catalyst may provide high activity and high acrylonitrile selectivity.

[0067] Method for producing a catalyst for ammoxidation reaction

[0068] The above manufacturing method comprises the steps of manufacturing a mixture of catalyst precursors such that the molar ratio of metals satisfies the stoichiometric molar ratio of Chemical Formula 1 below, pulverizing the mixture of catalyst precursors, drying the pulverized mixture, and calcining the dried mixture to manufacture a composite oxide, wherein the manufacturing method does not use nitric acid:

[0069] [Chemical Formula 1]

[0070] Mo1Bi a Fe b Co c Ni d O e

[0071] (In Chemical Formula 1, a, b, c, d, e, and f are each the molar ratio of each element relative to 1 mole of molybdenum, a is 0.05 or more and 0.20 or less, b is 0.05 or more and less than 0.15, c is 0 or more and 0.25 or less, d is 0.52 or more and 0.75 or less, and e is the number of oxygen atoms required to satisfy the valence of other elements present.)

[0072] In the manufacture of conventional ammonia oxidation catalysts, whether using co-precipitation or impregnation methods, the pH of the catalyst precursor slurry must be adjusted. This requires the addition of acids such as nitric acid. However, this nitric acid requires post-catalyst processing and can be toxic to humans and the environment if leaked.

[0073] On the other hand, the above manufacturing method is characterized by being a non-nitric acid manufacturing method that does not use nitric acid. Instead of using nitric acid, the manufacturing method mixes a catalyst precursor to prepare a mixture, pulverizes the mixture of the catalyst precursor, and then dries and calcines the mixture to produce a catalyst for ammoxidation reaction. The pulverization can enable the production of a catalyst that can increase the selectivity and yield of acrylonitrile even without using nitric acid, which is conventionally used in catalyst production.

[0074] The above manufacturing method according to one embodiment can be easily used to manufacture a catalyst for ammoxidation reaction having the composition of the above chemical formula 1.

[0075] The above manufacturing method comprises the steps of preparing a mixture of the catalyst precursor, pulverizing the mixture of the catalyst precursor, drying the pulverized mixture, and calcining the dried mixture. This is described in detail below.

[0076] Process for preparing a mixture of catalyst precursors

[0077] The catalyst precursor is mixed so as to satisfy the stoichiometric molar ratio of the above chemical formula 1.

[0078] The catalyst precursor for metal molybdenum may include at least one of ammonium molybdate, molybdenum tetrachloride oxide, molybdenum hexacarbonyl, and molybdenum chloride. Preferably, ammonium molybdate may be used.

[0079] The catalyst precursor for metal bismuth may include one or more of bismuth nitrate, bismuth citrate, bismuth chloride, and bismuth acetate. Preferably, bismuth nitrate may be used.

[0080] The catalyst precursor for metallic iron may include one or more of iron nitrate, iron chloride, iron acetylacetonate, and iron acetate. Iron nitrate may be preferably used.

[0081] The catalyst precursor for metallic cobalt may include one or more of cobalt nitrate, cobalt acetate, cobalt hydroxide, cobalt chloride, and cobalt acetylacetonate. Preferably, cobalt nitrate may be used.

[0082] The catalyst precursor for metallic nickel may include one or more of nickel nitrate, nickel chloride, nickel carbonate, and nickel acetylacetonate. Nickel nitrate may be preferably used.

[0083] Process of crushing a mixture of catalyst precursors

[0084] The mixture of the catalyst precursors prepared above can be finely divided by a grinding process. In the present invention, the catalyst is prepared by grinding the mixture in a container and then drying and calcining without using nitric acid.

[0085] For this purpose, the grinding process of the mixture of catalyst precursors can be performed using ball milling. Ball milling has been confirmed to be a useful method for preparing the catalyst of the above-described chemical formula 1 without using nitric acid.

[0086] Ball milling is not particularly limited, but can be performed using a container and balls made of zirconia. Ball milling can be performed at a milling speed of 10 to 30 Hz. In the above range, the catalyst of formula 1 can be manufactured in a high yield. Ball milling can be performed for 10 to 60 minutes, preferably 20 to 50 minutes. In the above range, the catalyst of formula 1 can be manufactured in a high yield. Ball milling can be performed at room temperature, for example, 20 to 50°C, for example, 20 to 30°C. In the above range, the catalyst of formula 1 can be manufactured in a high yield.

[0087] The above grinding process may be performed on the mixture of the catalyst precursor alone, but may also be performed with the addition of silica acting as a carrier. The carrier may be included in the final catalyst manufactured in a ratio of 50 to 90 wt% of the composite oxide: carrier: 10 to 50 wt%, out of a total of 100 wt% of the composite oxide and carrier.

[0088] The above-described grinding process may be performed solely on the mixture of the catalyst precursors, but depending on the properties of the catalyst precursors, it may also be performed with one or more additional ingredients, such as water or alcohol. Water or alcohol can facilitate the preparation of the catalyst by allowing the solid catalyst precursors to coagulate well with each other. For example, the alcohol may be an alcohol having 1 to 5 carbon atoms, preferably ethanol.

[0089] Process of drying the crushed mixture

[0090] This is a process for obtaining a carrier on which a catalyst precursor is supported by drying the above-mentioned pulverized mixture under a predetermined pressure.

[0091] Drying can be performed in one pass, but can also be performed multiple times, two or more times.

[0092] The above drying can be performed at atmospheric pressure at 60 to 120°C for 10 to 20 hours. During this process, water or alcohol added during the grinding process can be removed, leaving only the catalyst precursor on the carrier.

[0093] Process of heat-treating (calcining) a dried mixture

[0094] Finally, the dried mixture, i.e., the carrier on which the catalyst precursor is supported, is calcined at a temperature range of 500 to 700°C for 2 to 5 hours to finally obtain a catalyst.

[0095] However, the above drying and firing conditions are merely examples, and any condition that can sufficiently remove the solvent from the inside of the carrier and oxidize the metal precursor is sufficient.

[0096] Figure 1 illustrates a series of practical steps for manufacturing the catalyst of the present invention.

[0097] Referring to FIG. 1, a catalyst precursor (a metal bismuth precursor, a metal molybdenum precursor, and optionally a metal iron precursor, a metal cobalt precursor, and a metal nickel precursor) is introduced to prepare a mixture of catalyst precursors, and the mixture is pulverized by ball-milling, and then the pulverized mixture is dried and heat-treated (calcined).

[0098] Ammonium oxidation method

[0099] In another embodiment of the present invention, a method for ammoxidation of propylene is provided, comprising the step of reacting propylene and ammonia in a reactor in the presence of a catalyst of the above-described embodiment.

[0100] The catalyst of the above embodiment has high activity and high temperature stability, and can be used in the ammoxidation reaction of propylene to increase the selectivity of acrylonitrile and the yield of acrylonitrile.

[0101] In one specific example, the ammoxidation reaction can be performed using a continuous flow fixed bed reactor.

[0102] In the ammoxidation reaction, propylene (C3H6) : ammonia (NH3) can be mixed in a molar ratio of 1:1 to 1:2 and reacted in the presence of a catalyst. In the above range, it has high activity and high temperature stability, and can be used in the ammoxidation reaction of propylene to increase the selectivity and yield of acrylonitrile.

[0103] Air may be additionally included in the ammoxidation reaction. Specifically, propylene (C3H6): ammonia (NH3): Air may be mixed in a molar ratio of 1:1 to 2:5 to 15. Within the above range, it has high activity and high temperature stability, and can be used in the ammoxidation reaction of propylene to increase the selectivity and yield of acrylonitrile.

[0104] In the ammoxidation reaction, the catalyst may be included in an amount of 0.01 to 1 part by weight per 100 parts by weight of the total of propylene and ammonia. Within the above range, the catalyst has high activity and high temperature stability, and can be used in the ammoxidation reaction of propylene to increase the selectivity and yield of acrylonitrile.

[0105] In one specific example, the ammoxidation reaction for producing acrylonitrile from propylene can be performed at 400 to 500°C, for example, 430°C. In this range, the ammoxidation reaction of propylene has high activity and high temperature stability, and can be used to increase the selectivity and yield of acrylonitrile.

[0106] In the ammoxidation reaction, silica beads may be mixed in an amount of 1 to 3 times, for example 2 times, the amount of catalyst used to control the heat generated during the ammoxidation reaction.

[0107]

[0108] The present invention will be described in more detail below through examples. However, these examples are intended to exemplify the present invention and the scope of the present invention is not limited to these examples.

[0109]

[0110] Example 1

[0111] A catalyst comprising a composite oxide composed of Mo, Bi, Fe, Co, and Ni, wherein the molar ratio of metals in the catalyst is such that when Mo is 1, Bi is 0.05, Fe is 0.05, Co is 0.10, and Ni is 0.52.

[0112] A catalyst precursor mixture was prepared by mixing 2.229 g of ammonium molybdate, 0.303 g of bismuth nitrate, 0.258 g of iron nitrate, 0.367 g of cobalt nitrate, and 1.929 g of nickel nitrate in a vessel equipped with a ball mill. Then, SiO2 in an amount corresponding to 40 wt% of the total catalyst weight was additionally placed in the vessel. The mixture was pulverized by rotating the ball mill at 20 Hz for 30 minutes to prepare a pulverized mixture. The pulverized mixture was dried in an oven (temperature 100°C) for 12 hours and calcined at 530°C for 5 hours to prepare a composite oxide catalyst. No nitric acid was used in the preparation of the catalyst.

[0113]

[0114] Example 2

[0115] Substantially the same method as in Example 1 was performed except that the input contents of ammonium molybdate, bismuth nitrate, iron nitrate, cobalt nitrate, and nickel nitrate were changed. From this, a catalyst was prepared consisting of Mo, Bi, Fe, Co, and Ni, and the molar ratio of the metals in the catalyst was such that when Mo was 1, Bi was 0.20, Fe was 0.05, Co was 0.10, and Ni was 0.63.

[0116]

[0117] Example 3

[0118] Substantially the same method as in Example 1 was performed except that the input contents of ammonium molybdate, bismuth nitrate, iron nitrate, cobalt nitrate, and nickel nitrate were changed. From this, a catalyst was prepared consisting of Mo, Bi, Fe, Co, and Ni, and the molar ratio of the metals in the catalyst was such that when Mo was 1, Bi was 0.07, Fe was 0.05, Co was 0.10, and Ni was 0.63.

[0119]

[0120] Example 4

[0121] Substantially the same method as in Example 1 was performed except that the input contents of ammonium molybdate, bismuth nitrate, iron nitrate, cobalt nitrate, and nickel nitrate were changed. From this, a catalyst was prepared consisting of Mo, Bi, Fe, Co, and Ni, and the molar ratio of the metals in the catalyst was such that when Mo was 1, Bi was 0.11, Fe was 0.09, Co was 0.10, and Ni was 0.63.

[0122]

[0123] Example 5

[0124] Substantially the same method as in Example 1 was performed except that the input contents of ammonium molybdate, bismuth nitrate, iron nitrate, cobalt nitrate, and nickel nitrate were changed. From this, a catalyst was prepared consisting of Mo, Bi, Fe, Co, and Ni, and the molar ratio of the metals in the catalyst was such that when Mo was 1, Bi was 0.19, Fe was 0.05, Co was 0.10, and Ni was 0.63.

[0125]

[0126] Comparative Example 1

[0127] Substantially the same method as in Example 1 was performed except that the input contents of ammonium molybdate, bismuth nitrate, iron nitrate, cobalt nitrate, and nickel nitrate were changed. From this, a catalyst was prepared consisting of Mo, Bi, Co, and Ni, and the molar ratio of the metals in the catalyst was such that when Mo was 1, Bi was 1, Fe was 0, Co was 40, and Ni was 40.

[0128]

[0129] Comparative Example 2

[0130] Substantially the same method as in Example 1 was performed except that the input contents of ammonium molybdate, bismuth nitrate, iron nitrate, cobalt nitrate, and nickel nitrate were changed. From this, a catalyst was prepared consisting of Mo, Bi, Co, and Ni, and the molar ratio of the metals in the catalyst was such that when Mo was 1, Bi was 0.03, Fe was 0, Co was 0.55, and Ni was 0.28.

[0131]

[0132] Comparative Example 3

[0133] Substantially the same method as in Example 1 was performed except that the input contents of ammonium molybdate, bismuth nitrate, iron nitrate, cobalt nitrate, and nickel nitrate were changed. From this, a catalyst was prepared consisting of Mo, Bi, Fe, Co, and Ni, and the molar ratio of the metals in the catalyst was such that when Mo was 1, Bi was 0.03, Fe was 0.32, Co was 0.70, and Ni was 0.40.

[0134]

[0135] Comparative Example 4

[0136] A catalyst was manufactured in which the ratio of each metal was 1 for Mo, 0.05 for Bi, 0.33 for Fe, 0.58 for Co, and 0 for Ni.

[0137] A catalyst was prepared by adding 2.475 g of bismuth nitrate, 0.594 g of ammonium molybdate, and 0.684 g of iron nitrate to 60 ml of distilled water, adding 10 ml of HNO3, and completely dissolving the solution, drying it through rotary evaporation, and calcining it at 530°C for 5 hours.

[0138]

[0139] Comparative Example 5

[0140] A catalyst was manufactured in which the metal ratios of each catalyst composition were 1 for Mo, 0.05 for Bi, 0.33 for Fe, 0.58 for Co, and 0 for Ni. The composition of the manufactured catalyst was the same as that of Comparative Example 4. However, the catalyst was manufactured in substantially the same manner as in Example 1, except that the content of each catalyst precursor was changed.

[0141]

[0142] Comparative Example 6

[0143] A catalyst was prepared in the same manner as in Example 1, except that the molar ratio of the metal elements in the catalyst was changed as shown in Table 1 below.

[0144]

[0145] Comparative Example 7

[0146] A catalyst was prepared in the same manner as in Example 1, except that the molar ratio of the metal elements in the catalyst was changed as shown in Table 1 below.

[0147]

[0148] Comparative Example 8

[0149] A catalyst was prepared in the same manner as in Example 1, except that the molar ratio of the metal elements in the catalyst was changed as shown in Table 1 below.

[0150]

[0151] Comparative Example 9

[0152] A catalyst was prepared in the same manner as in Example 1, except that the molar ratio of the metal elements in the catalyst was changed as shown in Table 1 below.

[0153]

[0154] Evaluation of selectivity and yield of acrylonitrile by ammoxidation using a catalyst

[0155] The ammoxidation reaction was performed using a continuous-flow fixed-bed reactor. The reactants were a mixture of propylene (C3H6), NH3, and air in a molar ratio of 1:1.2:9.5, fed at a flow rate of 20 ml / min. 1.0 g of catalyst was used. To control exotherm generation, silica beads were mixed in an amount twice the mass of the introduced catalyst.

[0156] A reaction capable of producing acrylonitrile from propylene was carried out at 430°C using a continuous flow fixed bed reactor.

[0157] Each ammoxidation product of the examples and comparative examples was analyzed using a chromatograph (Gas chromatography, manufacturer: Agilent, equipment name: HP 6890 N) equipped with a FID (Flame Ionization Detector) and a TCD (Thermal conductivity detector).

[0158] Specifically, products such as ethylene, hydrogen cyanide, acetaldehyde, acetonitrile, and acrylonitrile were analyzed using FID, and gaseous products such as NH3, O2, CO, and CO2 and unreacted propylene were analyzed using TCD, thereby obtaining the mole number of propylene reacted and the mole number of ammoxidation products in each of the examples and comparative examples.

[0159] In addition to the analysis results, the number of moles of supplied propylene was substituted into 1 and 2 below to calculate the conversion rate of propylene and the selectivity of acrylonitrile, a product of the ammoxidation reaction of propylene, and the calculated values ​​are shown in Table 1:

[0160] [Formula 1]

[0161] Selectivity of acrylonitrile (%) = 100 x (number of moles of acrylonitrile produced) / (number of moles of propylene reacted)

[0162] Selectivity of acrylonitrile catalyst composition Example 1 Mo1Bi 0.05 Fe 0.05 Co 0.10 Ni 0.52 O 4.08 84.2 Example 2Mo1Bi 0.20 Fe 0.05 Co 0.10 Ni 0.63 O 3.75 80.3 Example 3Mo1Bi 0.07 Fe 0.05 Co 0.10 Ni 0.63 O 3.75 82.25 Example 4Mo1Bi 0.11 Fe 0.09 Co 0.10 Ni 0.63 O 4.42 82.43 Example 5Mo1Bi 0.19 Fe 0.05 Co 0.10 Ni 0.63 O 4.42 82.58 Comparative Example 1Mo1Bi1Fe0Co 40 Ni 40 O e 65.56 Comparative Example 2Mo1Bi 0.03 Fe0Co 0.55 Ni 0.28 O e 66.33 Comparative Example 3Mo1Bi 0.03 Fe 0.32 Co 0.70 Ni 0.40 O e 75.84 Comparative Example 4Mo1Bi 0.05 Fe 0.33 Co 0.58 Ni0O e73.90 Comparative Example 5Mo1Bi 0.05 Fe 0.33 Co 0.58 Ni0O e 78.20 Comparative Example 6Mo1Bi 0.01 Fe 0.09 Co 0.25 Ni 0.63 O e 70.66 Comparative Example 7Mo1Bi 0.05 Fe 0.21 Co 0.25 Ni 0.63 O e 72.68 Comparative Example 8Mo1Bi 0.05 Fe 0.09 Co 0.40 Ni 0.63 O e 72.48 Comparative Example 9Mo1Bi 0.05 Fe 0.09 Co 0.25 Ni 0.28 O e 73.98

[0163] *In Table 1 above, “Oe” in Comparative Examples 1 to 9 can be measured using Rietveld method analysis data, and showed a range substantially similar to Examples 1 to 5.

[0164]

[0165] As shown in Table 1 above, the ammoxidation catalyst of the present invention can increase the selectivity of acrylonitrile when producing acrylonitrile through ammoxidation and reduce the selectivity of side reactions that cause problems in the ammoxidation process. In addition, since no nitric acid is used in the production of the ammoxidation catalyst, it is friendly to humans and the environment.

[0166] On the other hand, the catalyst of the comparative example provided a significantly lower effect compared to the effect obtainable from the ammoxidation reaction catalyst of the present invention described above.

[0167]

[0168] Simple modifications or changes of the present invention can be easily implemented by a person having ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims

1. As a catalyst for ammoxidation reaction for producing acrylonitrile, The catalyst for the ammoxidation reaction above comprises a complex oxide, and the complex oxide is represented by the following chemical formula 1: A catalyst for the ammoxidation reaction for producing acrylonitrile: [Chemical Formula 1] I1Bi a Want b Co c In d SHE e (In Chemical Formula 1, a, b, c, d, e, and f are each the molar ratio of each element relative to 1 mole of molybdenum, a is 0.05 or more and 0.20 or less, b is 0.05 or more and less than 0.15, c is 0 or more and 0.25 or less, d is 0.52 or more and 0.75 or less, and e is the number of oxygen atoms required to satisfy the valence of other elements present.) 2. A catalyst for ammoxidation reaction in the first paragraph, wherein the ratio of the molar ratio of nickel to the molar ratio of cobalt in the chemical formula 1 is 4 to 8.

3. A catalyst for ammoxidation reaction in the first paragraph, wherein the ratio of the molar ratio of bismuth to the molar ratio of iron in the chemical formula 1 is 1 to 5.

4. In the first paragraph, the catalyst for the ammoxidation reaction further includes a carrier, The above carrier is a catalyst for ammoxidation reaction, comprising silica.

5. In the fourth paragraph, the catalyst for ammoxidation reaction, wherein the composite oxide and the carrier are included in a total of 100 wt%, and the composite oxide: carrier is included in a ratio of 50 to 90 wt%: 10 to 50 wt%.

6. A method for producing a catalyst for ammoxidation reaction for producing acrylonitrile, A step of preparing a mixture of catalyst precursors so that the molar ratio of metals satisfies the stoichiometric molar ratio of Chemical Formula 1 below, pulverizing the mixture of catalyst precursors, drying the pulverized mixture, and calcining the dried mixture to prepare a composite oxide of Chemical Formula 1 below, The above manufacturing method does not use nitric acid, Method for preparing a catalyst for ammoxidation reaction: [Chemical Formula 1] I1Bi a Want b Co c In d SHE e (In Chemical Formula 1, a, b, c, d, e, and f are each the molar ratio of each element relative to 1 mole of molybdenum, a is 0.05 or more and 0.20 or less, b is 0.05 or more and less than 0.15, c is 0 or more and 0.25 or less, d is 0.52 or more and 0.75 or less, and e is the number of oxygen atoms required to satisfy the valence of other elements present.) 7. A manufacturing method according to claim 6, wherein the crushing is performed by ball milling.

8. A manufacturing method according to claim 7, wherein the ball milling is performed at a milling speed of 10 to 30 Hz, a milling temperature of 20 to 50°C, and a milling time of 10 to 60 minutes.

9. A manufacturing method in the 6th paragraph, wherein the grinding is performed in a state in which at least one of water and alcohol is additionally included in the mixture of the catalyst precursor.

10. A method for ammoxidation of propylene, comprising a step of reacting propylene and ammonia in the presence of a catalyst according to any one of claims 1 to 5.

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