TW200417408A - Improved catalyst for the manufacture of acrylonitrile - Google Patents

Abstract

A catalyst comprising a complex of catalytic oxides comprising rubidium, cerium, chromium, iron, bismuth, molybdenum, and at least one of nickel or nickel and cobalt, optionally magnesium, and optionally one of phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, thallium, boron, germanium, tungsten calcium, wherein the relative ratios of these elements are represented by the following general formula: RbaCebCrcMgdAeFefBigYhMo12Ox wherein A is Ni or the combination of Ni and Co, Y is at least one of P, Sb, Te, Li, Na, K, Cs, Tl, B, Ge, W, Ca, Zn, a rare earth element, or mixtures thereof, a is about 0.01 to about 1, b is about 0.01 to about 3, c is about 0.01 to about 2, d is 0 to about 7, e is about 0.01 to about 10, f is about 0.01 to about 4, g is about 0.05 to about 4, h is 0 to about 3, x is a number determined by the valence requirements of the other elements present, wherein "b"+"c" is greater than "g" and wherein the catalyst is substantially free of manganese, a noble metal and vanadium. The catalyst is useful in processes for the ammoxidation of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile and mixtures thereof, respectively.

Description

200417408 (1) Description of the invention: ‘[Technical Field of the Invention] Field of the Invention The present invention relates to an improved catalyst which can be used for the ammoxidation of an unsaturated hydrocarbon compound 5 to a corresponding unsaturated clear. In particular, the present invention is directed to a method and a catalyst which can be used for the ammoxidation of propylene and / or isobutylene individually to propylene and / or methacrylic. More particularly, the invention relates to a novel and improved ammonia oxidation catalyst, which contains at least one kind of iron, bismuth, magnesium, at least A complex of nickel or nickel and catalytic oxides of cobalt, thallium, thallium, and chromium. BACKGROUND OF THE INVENTION Oxide catalysts that specifically contain iron, grades and thorium are used to promote the reaction with the appropriate element 15. These catalysts have been used for a long time to increase the temperature and the presence of ammonia and oxygen (usually from air). Below, acrylic acid is produced by converting propylene. In particular, British patent case number: 1434675, U.S. patent case number: 4,766,232, 4,377,534, 4,040,978, 4,168,246, 5,223,469, and 4,863,891 are individual 20. These are the secrets of the Group VIII elements that can improve the preparation of acrylics-turn- Iron catalyst. In addition, U.S. Patent No. 4,190,608 discloses similar iron, secret and key catalysts that can be used to enhance the oxidation of dilute hydrocarbons. U.S. Patent Nos. 5,093,299, 5,212,137, 5,658,842, and 5,834,394 are targeted at these silk mesh iron enhancement catalysts that exhibit high acrylonitrile yields. 6 200417408 An object of the present invention is a novel catalyst comprising a unique combination of promoters, thereby enabling the catalyst to catalyze the ammoxidation of propylene, isobutylene or a mixture thereof to produce propylene, methacrylic and When mixed, it will have better efficacy. [Summary of the Invention] Summary of the Invention The present invention is directed to a method and a catalyst which can be used for the ammoxidation of propylene and / or isobutylene individually to propylene and / or methacrylic. 10 In a specific example, the catalyst of the present invention includes a composite composed of catalytic oxides, the catalytic oxides include: # 0, rhenium, chromium, magnesium, iron, wire, molybdenum, and at least one nickel Or nickel and cobalt, and the relative proportions of these elements are expressed by the following formula: RbaCebCrcMgdAeFefBigM〇i20 × 15 where A is nickel (Ni) or a combination of nickel (Ni) and cobalt (Co), and a is approximately 0.01 to about 1, b is about 0.01 to about 3, c is about 0.01 to about 2, d is about 0.01 to about 7, 20 e is about 0.01 to about 10, f is about 0.01 to about 4, and g is about 0.05 To about 4, X is a number determined according to the price requirements of other existing elements, where " b " + 〃c〃 is greater than 〃g〃, and where the catalyst does not substantially contain 7 slits, a precious metal or vanadium. In a second specific example of the present invention, the catalyst of the present invention comprises a composite composed of a catalytic oxide, the catalytic oxide comprising: thorium, thorium, chromium, magnesium, iron, bismuth, molybdenum, and at least one Nickel or nickel and cobalt, and optionally one of phosphorus, antimony, tellurium, sodium, lithium, potassium, planer, thorium, boron, and crane's calcium, wherein the relative proportions of these elements are expressed by the following formula: RbaCebCrcMgdAeFefBigYhM. i2ox where A is nickel (Ni) or a combination of nickel (Ni) and cobalt (Co), and Y is at least one of phosphorus (P), antimony (Sb), tellurium (Te), lithium (Li), sodium (Na ), Unloading (K), cesium (Cs), rubidium (τΐ), shed (B), germanium (Ge), tungsten (W), calcium (Ca), zinc (Zn), a rare earth element, or a mixture thereof, a is about 0.001 to about 1, b is about 0.00 to about 3, c is about 0.00 to about 2, d is about 0.00 to about 7, and e is about 0.0 to About 10, f is about 0.01 to about 4, g is about 0.05 to about 4, h is about 0 to about 3, and X is a depending on other existence elements where 〃b〃 + 〃c〃 is greater than, manganese, a Precious metals or vanadium. The number of primes is required to determine the number, and the catalyst does not substantially include the catalyst of the present invention, and includes a composite of the catalytic oxide containing the catalytic oxide in the third embodiment of the present invention. 200417408, plutonium, chromium, iron, Syria: molybdenum, and at least one nickel or nickel and cobalt, and optionally a scale, antimony, tellurium, sodium, warp, bell, cesium, indium, paste, calcium, calcium , Where the relative ratio of these elements is expressed by the following general formula: RbaCebCrcAeFefBigYhMo12Ox 5 where A is nickel (Ni) or a combination of nickel (Ni) and cobalt (Co),

Y is at least one of phosphorus (P), antimony (Sb), tellurium (Te), sodium (Na), lithium (Li), potassium (K), cesium (Cs), rubidium (T1), boron (B), germanium (Ge), tungsten (w), office (Ca), zinc (Zn), a rare earth element, or a mixture thereof, a is about 0.01 to about 1, 10 b is about 0.01 to about 3, and c is about 0.01 To about 2, e is about 0.01 to about 10, f is about 0.01 to about 4, g is about 0.05 to about 4, 15 h is about 0 to about 3,

X is a number determined according to the valence requirements of other existing elements, where 〃b & + " c " is greater than " g〃, and wherein the catalyst does not substantially contain manganese, a precious metal or Kay. The catalyst of the present invention is also directed to a variety of methods which can be used to convert rare species selected from the group consisting of: 20, propylene, isobutylene, or mixtures thereof, and individually convert them to acrylic, methylpropene, and mixtures thereof. These methods involve reacting a gas containing oxygen molecules and ammonia with these olefins in the gas phase and an elevated temperature and pressure in the presence of a mixed metal oxide catalyst, where the catalyst is As described above. 9 200417408 I: Detailed description of the preferred embodiment 3 The present invention is a novel catalyst comprising a unique combination of promoters, thereby enabling the catalyst to catalyze the ammoxidation of propylene, isobutene 5 or a mixture thereof individually. When acrylic acrylonitrile, methacrylic acrylonitrile and mixtures thereof are produced, they have better efficacy. In a specific example, the catalyst of the present invention comprises a composite composed of catalytic oxides, the catalytic oxides include: I such as, rhenium, chromium, town, iron, wire, molybdenum, and at least one nickel or The relative proportions of nickel to Si and 10 of these elements are expressed by the following formula:

RbaCebCrcMgdAeFefBigM0i20x where A is nickel (Ni) or a combination of nickel (Ni) and cobalt (Co), a is about 0.01 to about 1, b is about 0.01 to about 3, 15 c is about 0.01 to about 2, d is about 0.01 to about 7, e is about 0.01 to about 10, f is about 0.01 to about 4, g is about 0.05 to about 4, 20, X is a number determined according to the price requirements of other existing elements, where 〃B〃 + 〃c〃 is larger than 〃g〃, and wherein the catalyst does not substantially contain manganese, a precious metal, or vanadium. In another specific example, " b〃 is also greater than 〃c〃. In another specific example of the present invention, 〃a〃 is (K05 to 0.3. In yet another specific example of the present invention, the catalyst of the present invention includes 10 200417408 composites composed of catalytic oxides. The catalyst Sexual oxides include: materials, decoration, chromium, town, iron, station, iron, and at least one nickel or nickel and cobalt, and optionally one of phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, rubidium, The relative proportions of boron, tungsten, and calcium are expressed by the following general formula:

RbaCebCrcMgdAeFefBigYhMo12Ox where A is nickel (Ni) or a combination of nickel (Ni) and cobalt (Co), and Y is at least one of phosphorus (P), antimony (Sb), tellurium (Te), via (Li), sodium (Na), Potassium (K), cesium (Cs), Ming (T1), shed (B), germanium (Ge), tungsten (W), about (Ca), zinc (Zn), a rare earth element, or a mixture thereof, a is About 0.01 to about 1, b is about 0.01 to about 3, c is about 0.01 to about 2, d is about 0.01 to about 7, 15 e is about 0.01 to about 10, and f is about 0.01 to About 4, g is about 0.05 to about 4, h is about 0 to about 3, X 疋 ί /, there is a number determined by the price requirement of the element, 20

Where b + V'A is at V 'and wherein the catalyst is substantially free of!,-A kind of precious metal or metal. In another specific example, " b " is also greater than " (in another specific example of this Maoming, V is from 0.05 to 0.3. In the catalyst product described above, L) is added with a chromium atom. Push (Βι) '[meaning the state " 大 η "]. Assuming that the amount [in atomic] of plutonium (c 11 200417408 plus chromium (Cr) is less than the amount of bismuth (Bi), the catalyst does not have equivalent activity. In another specific example, the amount of plutonium (Ce) [by Atomic meter] Amount greater than chromium (meaning 〃b " greater than 〃c "]. The basic catalyst composition described in this case is a kind of rhenium, trim, chromium, 5 town, iron, wire, platinum, and at least A compound composed of nickel or nickel and its catalytic oxide. In addition to the specifically excluded elements, it may contain other elements or promoters. In a specific example, the catalyst of the present invention may contain one or more phosphorus, Antimony, hoof, nano, Wei, unload, cesium, Ming, shed, germanium, tungsten, calcium, zinc, and a rare earth element (defined in this case as lanthanum (La), thorium 10 (Pr), '(Nd), moment ( Pm), Pm (Sm), 铕 (Eu), Chaos (Gd), 铽 (Tb), Dy (Dy), '(Ho), 铒 (Er), 铥 (Tm), 镒 (Yb) ). In another specific example, the basic catalyst may not include magnesium. In another specific example, the catalyst contains a small amount of phosphorus, which has a beneficial effect Abrasion resistance of chemical agents. 15 In addition, for the conversion of propylene, ammonia, and oxygen to propylene oxide, it has been confirmed that the inclusion of certain elements is detrimental to the production of a catalyst with improved yield of propylene oxide. These elements are manganese and precious metals (when used in the present invention, "the precious metal rhenium means ruthenium, rhodium, palladium, osmium, iridium, and platinum) and vanadium. The catalyst contains a precious metal to promote ammonia oxidation. This reduction of 20% can be used to produce propylene-clear ammonia. Including starvation will produce a catalyst that has higher propylene feed reactivity and lower product selectivity, thereby generating more carbon oxides and lower Less acrylic. The inclusion of manganese in the catalyst will result in a lower yield of propylene. Therefore, the catalyst of the present invention described in this case does not substantially contain manganese, heavy metals or vanadium. For manganese and vanadium 12 200417408 'this case The meaning of "Xian Zhi Zhi" does not mean "has a comparative atomic ratio of less than 0 2 • 12. For a precious metal, the f shell used in this case does not contain" Means to have an atomic ratio of comparative indium lower than ⑽U2. Preferably, the catalyst of the present invention does not contain ferrous, precious 5 metals and / or hunger. M in ιυ 10 15 20 ......% Dan Wei mattress body (: ㈣ chemical agent contains-a Gu). Suitable leaks are oxygen cutting, oxidized emulsion, titanium oxide, or mixtures thereof.-A typical support is available as a catalyst base stone 俾, which produces- This kind of harder and more abrasion-resistant, 丨 = catalyst. 对于, for „applications, a kind of catalytic oxide compound suitable for the active age of two is far from the above) and the foundation stone is made of 4 Accepting the catalytic meaning of activity and hardness (wear resistance) is the key. Any increase in the active phase will increase the activity of the catalyst!! = The hardness of the catalyst. Typically, the carrier with the carrier is suspected to be 340 to 6 Gwt%. In one embodiment of the present invention, the agent can include as little as about 3 °% by weight of the support. In the other two embodiments of the invention, the catalyst having a support may include up to ^ 70wt% of the support. As an additive element, you may include one or several kinds of fossil evening sols containing urn, which is a support material to be incorporated into the catalyst. For the support example, the catalyst is to use a kind of oxygen cut sol to ‘, ·, sa. The colloidal particle size of the right silica gel is too small. The surface area of the colloid is too small.> The colloidal particle size of the colloidal particle, which is made of silica gel, -I: Π, is shown to reduce the selectivity displayed by the gel. When it is too large, the catalyst

13 Righteousness and abrasion. Typically, the average colloidal particles of oxygen-cutting sol are between about 15 nm and about 50 nm. In one specific example of the present invention, the diameter of the hole cut is about 1 mm, and can be as low as 8 nm: In another specific example of the present invention, the average colloidal particle size of the oxygen-cut sol is about KKW in another one. Specifically, the average diameter of the oxygen-sol-sol sol was about 20 nm. The catalyst of the present invention can be prepared by any of several catalyst preparation methods known to those skilled in the art. For example, catalysts can be made by coprecipitating various components. Thereafter, the co-precipitated mass can be dried and then ground to a suitable size. ^ Optionally, the co-precipitated material is formed into a slurry, and then spray-dried in accordance with conventional techniques. The catalyst d can be extruded into pellets or made into water-in-oil spheres as is well known in the art. For specific methods for preparing catalysts, please refer to U.S. Patent Nos .: 5,0093,299 = 4,863,891 and 4,766,232, which are incorporated herein by reference. In a specific example, the catalyst component of the present invention is combined with a support in the form of a slurry, and then the slurry is dried, or the catalyst component of the present invention is poured on silica or other supports. The catalyst-introduced filament may be an oxide or a salt which will form its oxide upon calcination. Like the other elements, the bismuth salt is preferably a water-soluble salt that makes the compound uniformly dispersible in the catalyst. Most preferred is bismuth nitrate. The iron component formulated into the catalyst can be obtained from any compound which forms iron as its oxide under calcination. Like other elements, the iron salt is preferably θ so that it can be uniformly dispersed in the water-soluble salt of the catalyst. The best is iron nitrate. 200417408 The catalyst component introduced into the catalyst can be any type of oxide, such as dioxide, trioxide, or heptaoxide. However, a salt that is hydrolyzable or decomposable for use as a platinum source is preferred. The best starting material is ammonium heptaplatinate. 5 Other required components of chelating agents and optional enhancers (e.g. nickel (Ni), starting (Co), magnesium (Mg), chromium (Cr), phosphorus (P), tin (Sn), Tellurium (Te), shed (B), germanium (Ge), zinc (Zn), indium (In), calcium (Ca), tungsten (w) can be obtained from any suitable source. For example: cobalt, nickel, and Magnesium can be introduced into the catalyst with its nitrate. In addition, the introduced magnesium can be an insoluble carbonate or hydroxide that produces 10 oxides under heat treatment. The ballast introduced into the catalyst can be an alkali metal Or alkaline earth metal or ammonium salt, but preferably phosphoric acid. Desired and optional catalyst test components (eg, Li (Li), sodium (Na), bell (K), cesium (Cs), sharp (T1 ) Or a mixture thereof can be introduced into the catalyst by producing an oxide oxide or salt under calcination. Preferably, 15 is used in the method of incorporating such elements into the catalyst, which is easy to use and easily soluble The salt (such as nitrate). The preparation of the catalyst of the present invention is typically a silica sol combined with a heptaplatinic acid hydrolysate / valley fluid, which is added to this compound. A slurry containing these compounds (preferably wall salts of other elements). The solid material is then dried to 20%, debased, and then calcined. Preferably, the catalyst is spray-dried in a At a temperature of 110-350C, it is more preferably at ii0-25 ° C, most preferably 110-180 ° C. The debasing temperature is preferably 〇〇_50 (Tc, more preferably 250- 450 ° C. Finally, a calcination temperature is in the range of 300-700. (:, Preferably in the range of 350-650 ° C. 15 200417408 The catalyst of the present invention can be used to select a compound selected from the group consisting of: propylene, isobutylene or a mixture thereof. Groups of olefins are individually converted to ammoxidation methods of acrylic acid, methacrylic acid, or mixtures thereof. This method is to make these olefins and a gas containing oxygen molecules in the presence of the catalyst of the present invention 5 The reaction between ammonia and ammonia is in the gas phase and at an elevated temperature and pressure. Although other types of reaction tanks (eg, pipeline reaction tanks) can be used, the ammonia oxidation reaction is preferably performed on a fluid-based bed In a reaction tank, for fluid-based bed reactions for the production of acrylonitrile It is well-known in the conventional arts. The applicable reaction tank is, for example, the design of the reaction tank provided in US Patent Case No. 3,230,246. The case is incorporated herein as reference material. The conditions of the ammoxidation reaction are also known in the arts. As you know, you can refer to, for example, US Patent Nos .: 5,093,299, 4,863,891, 4,767,878, and 4,503,001, which are incorporated herein by reference. Typically, the ammoxidation reaction is performed at elevated temperatures and in the presence of ammonia and oxygen to A fluid 15-bed catalyst to contact propylene or isobutylene, thereby producing propylene or methacrylic. Any type of oxygen supply can be used. For economic reasons, however, air is preferred. Typically, the feed oxygen to olefin mole ratio is in the range of 0.5: 1 to 4: 1, preferably in the range of 1: 1 to 3: 1. The ratio of the feed ammonia to olefin mole of the 9Π reaction can fall in the range of 0.5: 1 to 2: 1. In general, there is no upper limit for the ratio of ammonia to olefin mole, but for economic reasons, it usually does not exceed a 2: 1 ratio. A suitable feed ratio for the catalyst of the present invention to produce propylene from diene is a ratio of ammonia to propylene ranging from 0.9: 1 to 1.3: 1, and the ratio of air to propylene ranging from 8.0: 1 to 12.0: i 16 200417408. The catalyst of the present invention provides a high yield of acrylic acid by a relatively low ammonia to propylene feed ratio of about 1: 1 to about 1.05: 1. These "low ammonia reaction conditions" can help reduce the unreacted ammonia that resides in the reaction tank fluid, which is a reaction condition known as " ammonia depletion ", which can substantially reduce process costs. In particular, unreacted ammonia must be removed from the reaction tank effluent before the acrylic acid is recovered. The removal of unreacted ammonia is typically contacting the reaction tank effluent with sulfuric acid to produce ammonium sulfate, or contacting the reaction tank effluent with acrylic acid to produce ammonium acrylate, both of which lead to the need for treatment and / or disposal Process waste stream. 10 The ammoxidation reaction is carried out in a temperature range of about 260 ° C to 600 ° C, preferably 310 ° C to 500 ° C, and particularly preferably 350 ° C to 480 ° C. Although the contact time is not critical, it usually falls within the range of 0.1 to 50 seconds, preferably a contact time of 1 to 15 seconds. The reaction product can be recovered and purified by any method known to those skilled in the art. One method involves washing with cold water or a suitable solvent to remove the reaction product, followed by purification by distillation. The main use of the catalyst of the present invention is for the ammoxidation of propylene to propylene. However, the catalyst of the present invention is also useful for the oxidation of propylene to propylene 20 acid. This process is typically a two-stage process, in which propylene is' converted to primary acrylic acid 'in the presence of a catalyst in the first stage, and the acrolein is then' in a catalyst in the second stage In the presence of 'is converted to acrylic. The catalyst described in this case is suitable for use in the first stage, whereby the propylene is oxidized to acrolein. 17 Specific Specific Examples To illustrate the present invention, the catalysts of the present invention and similar but omitting one or more (or additionally including) catalysts that would be detrimental to the generation of acrylonitrile are evaluated under similar reaction conditions. These examples are for illustrative purposes only. Preparation catalyst Example 1: A catalyst having a chemical formula: 50wt% Ni5.o Mg2.〇Feu Bi0 45 Ce0.9 Cru Rb0.15M〇i2〇48.4 + 50wt% Si02 catalyst was prepared as follows: the following nitrate: iron nitrate ( Fe (N03) 3 · 9Η20) (69 · 752g), nickel nitrate (Ni (N03) 2 · 6Η20) (139 · 458g), magnesium nitrate (Mg (N03) 2 • 6H20) (49.186g), nitric acid Bismuth (Bi (N03) 3 · 5Η20) (20.937 grams), rhenium nitrate (RbN03) (2.122 grams), and diammonium osmium nitrate ((NH4) 2Ce (NO *) (a 50% solution of 94.654 grams), At ~ 70 ° C—and melted in a 1000 ml beaker. Dissolve ammonium heptamolybdate (ΑΗΜ) (203 · 219 g) in 310 ml of distilled water. To this solution add one dissolved in 20 ml of water. Chromium oxide (Cr03) (0.959 g). Following the melting of the metal nitrate, silicon oxide (a 28.% SiO 2 (SiO 2) solution of 871.08 g) was added. The resulting yellow slurry was then sprayed Dry. The prepared material is denitroted in air at 290 ° C / 3 hours, followed by 425 ° C / 3 hours, and then calcined at 570 ° C / 3 hours. Example 2: 50wt% Ni2.5Mg2.〇C〇2.5Fe1.8Bi〇 < 45Ce〇9Cr〇lRb〇15M〇i2〇48.4 + 50wt% SiO2 200417408 The catalyst is prepared as in Example 1. The catalyst formula is as follows: nitric acid Iron (Fe (N03) 3 · 9Η2〇) (69 · 737 g), nickel nitrate (Ni (N〇3) 2 · 6Η20) (69 · 714 g), magnesium nitrate (Mg (N〇3) 2 · 6Η2 〇) (49.176 g), cobalt nitrate (Co (N03) 2. 6Η2〇) (69.774 g), bismuth nitrate (Bi (N〇3) 3.5 5 5 2 0) (20.993 g), Rhenium nitrate (RbN03) (2.m g) and diammonium rhenium nitrate ((NH4) 2Ce (N〇3) 6) (a 50% solution of 94.634 g) at ~ 70 ° C-and melted in a 1000 ml In a beaker, dissolve ammonium heptamolybdate (ΑΗΜ) (203 · 175 g) in 310 ml of distilled water. Add a solution of chromium trioxide (CrO3) (0.959 g) dissolved in 20 ml of water to this solution. Subsequent to the metal 10 After nitrate melting, add silicon oxide (796.178 grams of a 31.4% silicon dioxide (Si02) solution). Example 3: 50wt% Ni5.OMG2.〇Fei.8Bi.45Ce〇 < 9Cr〇.iLi〇 > 3Rb〇15M〇i2〇48.55 + 50wt% SiO2 15 The preparation of this catalyst is as the above example 1. The catalyst formulation is as follows: iron nitrate (Fe (N03) 3 · 9Η20) (69 · 632 g), nickel nitrate (Ni (N03) 2 · 6Η20) (139 · 219 g), magnesium nitrate (Mg (N03) 2 · 6Η20) (49 · 102g), lithium nitrate (LiN03) (1.981g), bismuth nitrate (Bi (N03) 3 · 5Η20) (20 · 901g), thorium nitrate (RbN03) (2.118g), and thorium nitrate Diammonium 20 ((NH4) 2Ce (N03) 6) (a 50% solution of 94.634 grams) at ~ 70 ° C-and melt in a 1000 ml beaker. Dissolve ammonium heptamolybdate (AHM) (202.87 g) in 310 ml of distilled water. To this solution was added a chromium trioxide (CrO3) (0.958 g) dissolved in 20 ml of water. Following the melting of the metal nitrate, oxidized stone (796.178 g of a 31.4% SiO2 solution) was added. 19 Embodiment 4:

50wt% Ni2.5Mg2. 0C02.5Fei.8Bi045Ce0.9Cr0.iP0.iW0.iRb0> 15M0 12 048.95 + 50 wt% Si0 2 The catalyst was prepared as in Example 1 above. The catalyst formulation is as follows: Ferric nitrate (Fe (N03) 3 · 9Η20) (68 · 936 g), nickel nitrate (Ni (N〇3) 2 · 6Η20) (68 · 914 g), magnesium nitrate (Mg (N 〇3) 2 · 6Η20) (48 · 611 g), cobalt acid (Co (N03) 2 · 6Η20) (68 · 973 g), bismuth nitrate (Bi (N〇3) 3 · 5Η20) (20 · 693 G), rhenium nitrate (RbNO3) (2.097 g), and diammonium rhenium nitrate ((NH4) 2Ce (N03) 6) (a 50% solution of 93.574 g) at ~ 70 ° C-and dissolved in a 100% Ml of beaker. Dissolve ammonium heptamate (ΑΜΜ) (200.842 g) in 310 ml of distilled water. To this solution was added a solution of phosphoric acid (Η3Ρ04) dissolved in 20 ml of water (1.093 grams per 85% solution), hexaammonium hexanoate, and chromium trioxide (CrO3) (0.948 grams). Following the melting of the metal nitrate, silicon oxide (796.178 g of a 31.4% silicon dioxide (SiO2) solution) was added. Example 5: 50wt% Ni5.0.Mg2.〇Fei.8Bi0.45Ce0.9Cr0.1Na〇 > 2Rb0 > 15M〇i2〇48 5 + 50wt% Si〇2 The preparation of this catalyst is as the above example 1. The catalyst formulation is as follows: iron nitrate (Fe (N03) 3 · 9Η20) (69 · 586 g), nickel nitrate (Ni (N〇3) 2 · 6Η20) (139 · 127 g), magnesium nitrate (Mg (N03) 2 · 6H2〇) (49 〇7 g), nitrate (NaN03) (1.626 g), bismuth nitrate (Bi (N03) 3 · 5η2〇) (2 · 888 g), nitrate nitrate (RbN〇3 ) (2.117 g), and diammonium diammonium ((NH4) 2Ce (N03) 6) (a 50% solution of 94.429 g) were melted together in a ~ 700 ° C 200417408 in a 1000 ml beaker. Dissolve ammonium heptamolybdate (ahm) ^ (202.736 g) in 310 ml of distilled water. To this solution was added chromium trioxide (CrO3) (0.957 g) dissolved in 20 ml of water. Following the dissolution of the metal nitrate, an oxidation second (796.178 grams of a 31.4% dioxide second, 5 (SiO 2) solution) was added. Example 6 · 50Wt% Ni5.0Mg2.0Fei.8Bi0.45Ce0.99Cr (UPolRb〇15m〇12〇48 must + 50wt% SiO2 This catalyst is prepared as in Example 1. The catalyst formulation is as follows: Lu 10 Lithium iron oxide (Fe (N03) 3 · 9Η20) (69 · 562 g), nickel nitrate (Ni (N〇3) 2 · 6Η2〇) (139 · 079 g), magnesium nitrate (Mg (N03) 2 · 6Η2〇 ) (49.053 g), nitrate nitrate (Bi (N03) 3.5Η2Ο) (20.881 g), thorium nitrate (RbN〇3) (2.07 g), and diammonium nitrate ((NH4) 2Ce (N03) 6) (a 50% solution of 94.397 grams) at ~ 70 ° C-and dissolved in a 1000 ml beaker. Dissolve ammonium heptamolybdate (ΑΗΜ) (202 · 667 g) in 310 ml of distilled water To this solution was added an acid (填 3PO4) dissolved in 20 ml of water (1.103 grams obtained from an 85% solution) and chromium trioxide (CrO3) (0.957 grams). Following the dissolution of the metal nitrate Add oxidized stone (796.178 grams of a 31.4% SiO2 (Si02) solution). 20 Comparative Example AD: A. 50wt% Ni5.〇Mg2.〇FeL8Bi.45Ce〇.9Rb〇.i5Mo12〇4825 + 5 〇wt% Si〇2 Β · 50wt% Ni5.〇Mg2OFe1.8Bi〇45Cr〇1Rb〇.15M o12〇466 + 50wt% Si〇2 C · 50wt% Ni5i〇Mg2.〇FeL8Bi〇45Ce0.9Cr0 > iK〇 > 15Mo12〇484 + 50wt% Si〇2 D · 50wt% Ni5.0.Mg2. F ^ i.8Bi〇.45Ce 0.9CrO.iCs 0.15M〇12〇484 + 50% by weight Si〇2 21 200417408 Using the preparation method described in Example 1 above, several kinds were similarly prepared at the time of preparation Omitting other catalysts of chromium, rubidium, or thorium, in Comparative Examples c and D, cesium [cesium shinate (CsN03, 2.797 g)] and potassium [potassium lithiata (KN〇3, 1.458) were used. G)] instead of 铷. 5 Comparative Example E · 50wt% Ni5.OMG2.〇Fe1.8Bi0.45Ce0.9Cr0.1Rb015Mn1.〇Mo12〇49. 4 + 50wt% SiO2 By the above Example 1 Catalyst preparation method, the catalyst of this example is added with manganese [manganese nitrate (Mn (N03) 2, a 51. 1% solvent of 32.699 grams)]. 10 Comparative Example F · SOwt ^ NiaMgaFeuBi ^ C ^ CrQ iRb〇i5pd〇ιΜ〇ΐ2〇4δ 5 + 50wt% SiO2 According to the method for preparing the catalyst of Example 1, the catalyst of this example is added with a precious metal palladium [palladium lithiarate (Pd (N03) 2, 2.2 g) ]. 15 Comparative Example G · SOw ^ NkoMguFeuBi ^ Ce. 9CrQ is π. 5M0i2〇㈣ + 50wt% SiO2 According to the method for preparing the catalyst of Example 1, the catalyst of this example is added with Kai [Beryllium Starch (NH4V03, 5.514 g)]. 20 Comparative Example Η: 50wt% Ni5, Mg, 〇Fe, 8Bi〇, 5Ce0.15cr0.3Rb〇15M〇i20〇47 2 + 50wt% Si02 using the preparation method described in Example 1, however, The atomic number of moles of thallium (Ce) plus chromium (Cr) is equal to the moles of bismuth (Bi). This catalyst 22 200417408. The formula of the chemical agent is as follows: ferric nitrate (Fe (N03) 3 · 9Η20) (72 · 939 g), nickel nitrate (Ni (N03) 2 · 6Η20) (145 · 83 g), magnesium nitrate (Mg (N03) 2 · 6Η20) (51 · 434 g), bismuth nitrate (Bi (N03) 3 · 5Η20) (21 · 894 g), thorium nitrate (RbN03) (2.219 g), and diammonium diammonium nitrate ( (NH4) 2Ce (N03) 6) 5 (a 50% solution of 16.496 g) at ~ 70 ° C-and melted in a 1000 ml beaker. Dissolve ammonium heptacupate (ΑΜΜ) (212.504 g) in 310 ml of distilled water. To this solution was added a chromium trioxide (CrO3) (3e009 g) dissolved in 20 ml of water. Following the melting of the metal nitrate, silicon oxide (871.08 g of a 28.75% silicon dioxide (Si02) solution) was added. 10 Comparative Example I: 50wt% Ni5.〇Mg2.〇Fei.8Bi0.45Ce〇.iCr〇.1Rb 0.15M〇i2〇46.8 + 50% wt% Si〇2 using the preparation described in Example 1 above The method, however, is the atomic number (Ce) plus the number (Cr) is less than the number (Bi). The formula of this catalyst is as follows: iron nitrate (Fe (N03) 3 · 9Η20) (73 · 642 g), nitrate (Ni (N03) 2 · 6 · 20) (147 · 23 g), magnesium nitrate (Mg ( N03) 2 · 6Η20) (51 · 93 g), bismuth nitrate (Bi (N03) 3 · 5Η2〇) (22 · 105 g), thorium nitrate (RbN03) (2.24 g), and diammonium nitrate ((NH4) 2Ce (NO3) 6) (11.104 grams of a 50% solution) at ~ 70 ° C-and melted in a 1000 milliliter 20 liter beaker. Dissolve ammonium heptamolybdate (ΑΜΜ) (214.553 g) in 310 ml of distilled water. To this solution was added a trioxide (CrO3) (1.03 g) dissolved in 20 ml of water. Following the melting of the metal nitrate, stone oxide (871.08 g of a 28.75% silicon dioxide (SiO2) solution) was added. Comparative Example J: 23 200417408 50wt% Ni5.OMg2.〇Fe1.8Bi2.0Ce0.9cr0.1Rb〇1 ^ ~ t% Si02 Using the preparation method described in Example 1 above, however, on an atomic basis, # (Ce) The amount of chromium (Cr) is equal to the amount of bismuth (Bi). The five components of this catalyst are as follows: ferric nitrate (Fe (N03) 3 · 9η2〇) (61 · 264 g), nickel nitrate (Nι (Ν〇3) 2 · 6Η20) (122 · 488 g), acid Thorium (Mg (N〇3) 2 · 6Η20) (43.201 g), nitric acid lit (Bi (N〇3) 3 · 5Η20) (81.732 g), and nitrate nitrate (RbN〇3) (1.863 g) And diammonium osmium nitrate ((NH4) 2Ce (NOA) (a 50% solution of 83.136 g)) at ~ 70 ° C-and dissolved in one; [00〇 · 10 liter beaker. Dissolve ammonium heptamolybdate (AΗM) (178.49 g) in 310 ml of distilled water. To this solution was added a solution of chromium trioxide (CrO3) (0.843 g) dissolved in 20 ml of water. Following the metal nitric acid After the salt was melted, silicon oxide (871.08 grams of a 28.75% silicon dioxide (SiO2) solution) was added. Test Catalyst 15 All tests were performed in a 40 cc fluid-based bed reactor. Propylene was produced using a 0.06 WWH (Italy) That is, the rate of propylene weight / catalyst weight / hour) was fed into the reaction tank. The pressure in the reaction tank was maintained at 10 psig Φ. The reaction temperature was 430 ° C. After the stabilization was completed for ~ 20 hours, a sample of the reaction product was collected.The effluent from the reaction tank was collected by bubble-type washing with cold hydrochloric acid (HC1) solution, 20 devices. The exhaust rate was measured with a soap film tester, and then-a gas analyzer equipped with a shunting column was used. A gas chromatograph was used to assist in the determination of the final exhaust gas composition. At the final recovery operation, all washing liquids were diluted to approximately 200 grams with distilled water. A quantitative amount of 2-butanone was used as a known standard 'And formulated as a ~ 50 grams of diluted liquid. In a gas chromatograph (GC) equipped with 24 flame ionizer and a crosslinked ethylene glycol (Carbowax) column. Analyze a 2μ1 sample. The amount of ammonia (NH3) is determined by titrating an excess of free hydrochloric acid (HC1) with a sodium hydroxide (NaOH) solution. The following sample illustrates the present invention. Table 1 Sample active phase composition Toatal c3 = Conv. Conv. To AN Sel. To AN 1 Wl5.〇Mg2.〇hei.8lii〇.45Ce〇.9Cr〇iRb〇15MO12O48 4 98.8 80.0 81.0 2 Ml2.5Mg 2.〇 ^ 〇2.5 Fei. 8Bi〇.45Ce〇 .9Cr〇.iRb〇i5M〇i2〇48.4 99.2 81.8 82.5 3 Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1L i03Rb015Mo12O48.55 98.8 79.9 81.4 4 Nl2.5Mg2.〇 ^ 〇2.5i :, ^ 1.8Bi〇.45Ce 0.9Cr0.iP〇iW〇.iRb〇.i5M〇i2〇48.95 99.7 80.9 81.2 5 Nl5.〇Mg2 .〇iHei.8Bi〇.45Ce0.9Cr0.iNa〇2Rb〇.i5M〇i2〇48.5 99.6 81.0 81.3 6 Mi5.〇Mg2.〇Fei.8Bi〇.45Ce0.9Cr0.iP0 > 1Rb. i5M〇i2〇48.65 99.6 82.3 82.6 A Ni5.0Mg2.0Fel.8Bia45ce0.9Rb0.15Mol2o48.25 99.4 79.3 79.9 B Ni5.〇Mg2.〇Fei.8Bi〇.45Cr〇.iRb〇.i5M〇i2〇46.6 91.2 75.8 83.1 C Ni5.〇Mg2. 0Fei.8Bi0.45Ce0.9Cr0.iK0.i5M0i2〇4e.4 99.7 77.6 77.8 D Ni5.0Mg2. 0Fei.8Bi0.45Ce0.99Cr. iCs〇.i5M〇i2〇48.4 96.8 69.6 72.0 E Ni5.〇Mg2.〇Fei.8Bi〇45Ce 0.9Cr0.iRb〇.i5Mni.〇M〇i2〇49.4 97.3 78.0 78.6 F Ni5.〇Mg2.Fei .8Bi〇.45Ce0.9Cr0.iRbai5Pd〇.iM〇i2〇48.5 99.3 78.7 81.4 G Ni5.0Mg2.0Fel. 8Bi0.45ce0.9cr0.lRb0.15v0.5Mol2o49.65 96.4 76.8 79.7 ΗNi5.OMg2. 〇Fei.8Bi〇.45Ce〇.i5Cr〇.3Rb〇.i5M〇i2〇47.2 93.5 77.9 83.3 I Ni5.〇Mg2.〇Fei.8Bi〇.45Ce〇.iCr〇.iRb〇.i5M〇i2 46.8 94.9 74.4 78.5 J Ni5.〇Mg2.〇Fei.8Bi2.〇Ce0.9Cr0.iRb〇.i5M〇i2〇46.8 97.7 78.8 80.7 Notes: 1 All test catalysts contain 50% active phase and 50% Silicon dioxide (Si02) 2 / Total C3 = Conv. &Quot; is the mole percentage of propylene that is passed into each product for each pass. 3. " Conv. To AN〃 is the mole percentage of each pass of propylene converted into propylene. 4. 〃Sel. To AN 〃 is the ratio of the percentage of propylene moire to the percentage of propylene moire. The catalyst composition of the present invention is unique in that it is substantially free of manganese, a precious metal or vanadium, and contains rhenium, Thorium, chromium, magnesium, iron, 200417408 bismuth, molybdenum, and at least one nickel or nickel and cobalt. This combination of elements in the relative proportions described in this case has not yet been used in a single ammonia oxidation catalyst formulation. As explained in Table 1, for the purpose of converting propylene to propylene oxide, the catalyst of the present invention exhibits a better combination of elements than those described in the patents containing similar (but not identical) exercises. Functions. More specifically, when propylene is exposed to an elevated temperature and the presence of ammonia and air, it does not contain ferrous metals, a precious metal, or hunger, and contains' gamma, decoration, metal, magnesium, iron, wire, molybdenum, and The effect of at least one nickel or nickel and nickel catalyst will show a higher overall conversion rate and acrylonitrile conversion rate than similar catalysts 10 which deviate from the scope of the present invention. Although the above description and the above specific examples are typical for implementing the present invention, for those skilled in the art, many changes, modifications and variations are obvious. Therefore, it is intended that all such changes, modifications, and alterations are general and fall within the broad meaning of the present invention and are defined by the scope of the attached application patent 15. [Simplified description of the drawing 3 None [Representative symbols of the main components of the drawing] Yi 26

Claims (1)

200417408 Scope of patent application: 1. A catalyst composition comprising a composite composed of catalytic oxides. The catalytic oxides include: rhenium, thorium, chromium, magnesium, iron, silk, and mesh. And at least one kind of nickel or nickel, and the relative proportion of these five elements is expressed by the following formula: RbaCebCrcMgdAeFefBigMo12Ox where A is nickel (Ni) or a combination of nickel (Ni) and cobalt (Co), a Is about 0.01 to about 1, b is about 0.01 to about 3, 10 c is about 0.01 to about 2, d is about 0.01 to about 7, e is about (L01 to about 10, f is about 0.01 to about 4, g Is about 0.05 to about 4, 15 X is a number 9 which depends on the valence requirements of other existing elements, where 〃b〃 + 〃c〃 is greater than 〃g〃, and wherein the catalyst does not substantially contain ferrous and precious metals 2. If the catalyst composition according to item 1 of the patent application scope, where b is less than c. 20 3. If the catalyst composition according to item 1 of the patent application scope, wherein the catalyst contains scales. The catalyst composition of 1 item The catalyst contains at least one kind of bell, decoration, sodium, or a mixture thereof. 5. The catalyst composition according to item 1 of the patent application scope, wherein the catalyst 27 includes t-supports selected from the group consisting of: oxygen cutting, oxygen She, oxidation oxide, titanium oxide or mixtures thereof. For example, if you apply for the catalyst composition of item 5 of the full-time application, the carrier is 30-70 wt% of the catalyst. For example, if you apply for the catalyst composition of item 1 of the patent scope, Wherein the silicon oxide contained in the catalyst composition has an average colloidal particle diameter between about 8 nm and about 100 nm. A catalyst composition includes a composite composed of a catalytic oxide, and the catalytic oxide includes : Thallium, Thallium, Chromium, Town, Iron, Bismuth, Molybdenum, and at least one kind of nickel or nickel and cobalt, and optionally, a kind of stone hoe, record, hoof, sodium, bell, potassium, cesium, snake, side, germanium , Crane, sentence, where the relative proportions of these elements are expressed by the following general formula: RbaCebCrcMgdAeFefBigYhM〇i2〇x where A is nickel (Ni) or a combination of nickel (Ni) and cobalt (Co), and Y is at least one phosphorus (P), antimony (Sb) Tellurium (Te), lithium (Li), sodium (Na), potassium (K), planer (Cs), Ming (T1), delete (B), germanium (Ge), tungsten (W), calcium (Ca), (Zn), a rare earth element, or a mixture thereof, a is about 0.01 to about 1, b is about 0.01 to about 3, c is about 0.01 to about 2, d is about 0 to about 7, and e is about 0.01 to About 10, f is about 0.01 to about 4, 200417408 g is about 0.05 to about 4, h is about 0 to about 3, and X is a number g that depends on the price requirements of other existing elements, 5 where " b 〃 + 〃c " is greater than V, and wherein the catalyst does not substantially contain ferrous metals, precious metals or hunger. 9. The catalyst composition as claimed in item 8 of the patent application, wherein b is less than c. 10. The catalyst composition as claimed in claim 8 wherein d is from about 0.01 to about 7.0. 10 11. The catalyst composition according to item 8 of the patent application, wherein the catalyst comprises scales 12. The catalyst composition according to item 8 of the patent application, wherein the catalyst comprises at least one bell, trim, sodium, or a mixture thereof. 13. The catalyst composition according to item 8 of the application, wherein the catalyst 15 comprises a support selected from the group consisting of: silica, alumina, hammer oxide, titanium oxide or a mixture thereof. 14. The catalyst composition according to item 13 of the patent application, wherein the supporting system is 30-70 wt% of the catalyst. 15. The catalyst composition according to item 8 of the patent application scope, wherein the catalyst 20 composition contains silicon oxide having an average colloidal particle size between about 8 nm and about 100 nm. 16. A method for individually converting an olefin selected from the group consisting of propylene, isobutylene, or a mixture thereof into acrylonitrile, methacrylonitrile, and mixtures thereof in a gas phase and a Under the elevated temperature and pressure of 29 200417408, and the presence of a catalyst, the reaction of an octaoxane-containing gas and ammonia with these olefins. The catalyst contains a composite of catalytic oxides, The catalytic oxide comprises: rhenium, thorium, chromium, iron, bismuth, molybdenum, and at least one nickel or nickel and cobalt, optionally magnesium, and optionally one phosphorus, antimony, tellurium, sodium, lithium, potassium , Cesium, rubidium, boron, tungsten, calcium, where the relative proportions of these elements are expressed by the following formula: RbaCebCrcMgdAeFefBigYhMo12Ox where A is nickel (Ni) or a combination of nickel (Ni) and cobalt (Co), and Y is at least A kind of phosphorus (P), antimony (Sb), tellurium (Te), lithium (Li), sodium (Na), potassium (K), planer (Cs), Ming (T1), boron (B), germanium (Ge) , Tungsten (W), calcium (Ca), rhenium (Zn), a rare earth element, or a mixture thereof, a is about 0.01 to about 1 , B is about 0.01 to about 3, c is about 0.01 to about 2, d is about 0 to about 7, e is about 0.001 to about 10, f is about 0.01 to about 4, and g is about 0.05 to about 4, h is about 0 to about 3, and X is a number g that depends on the price requirements of other existing elements, where " b " + " c " is greater than 〃g ", and wherein the catalyst is substantially free of 30 200417408 Contains manganese, a precious metal or hunger. 17. The method according to item 16 of the patent application, wherein b is less than c. 18. The method according to item 16 of the patent application, wherein d is about 0.01 to about 7.0. 5 19. The method of claim 16 in the scope of patent application, wherein h is 0. 20. The method of claim 16 in which the catalyst comprises phosphorus. 21. A method as claimed in claim 16 wherein the catalyst comprises at least one of a polymer, a decoration, a sodium, or a mixture thereof. 22. The method according to item 16 of the patent application, wherein the catalyst comprises a 10 support selected from the group consisting of: silica, alumina, zirconia, titania or a mixture thereof. 23. The method according to item 22 of the patent application, wherein the supporting system is 30-70% by weight of the catalyst. 24. The method according to item 16 of the patent application, wherein the catalyst composition 15 contains an average of silicon oxide. The colloidal particle size is between about 8 nm and about 100 nm. 200417408 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) Brief description of the element representative symbols of this representative diagram: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the features of the invention: RbaCebCrcMgdAeFefBigYhM〇i2〇x