CN107282060B - Acrylonitrile catalyst for ammoxidation process - Google Patents
Acrylonitrile catalyst for ammoxidation process Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to an acrylonitrile catalyst for an ammoxidation process, which mainly solves the problems of low selectivity and poor stability of a catalyst for propylene ammoxidation in the prior art. The invention adopts an ammoxidation process acrylonitrile catalyst, which comprises a carrier and active components containing the following general formula: a. theaBbCcNidFeeBifMo13.6Ox；Wherein A is selected from at least one of K, Rb and Cs; b is at least one selected from Ca, Mn, Co, Mg, Cr, W, P and Nb; c is at least one of rare earth elements; the carrier comprises silicon dioxide and a carrier modifier, and the carrier modifier is at least one of zirconium oxide and titanium oxide, so that the problem is well solved, and the method can be used in the industrial production of acrylonitrile by propylene ammoxidation.
Description
Technical Field
The present invention relates to an acrylonitrile catalyst for ammoxidation process.
Background
At present, the industrial production of preparing unsaturated nitrile by olefin ammoxidation still generally adopts a fluidized bed ammoxidation process, and a catalyst is taken as one of core technologies of the process, and the research and the improvement of the process are always paid attention. At present, the catalyst for preparing acrylonitrile by industrial propylene ammoxidation mainly comprises two types: Mo-Bi and Sb, wherein Mo-Bi catalysts dominate, reaching 95% of olefin oxidation markets, and the previous research and exploration mainly focuses on Mo-Bi catalysts. The oxidation-reduction performance of the catalyst is improved by introducing metal components with variable valence states, such as Fe, Ce and other elements, into the catalyst, and the recovery of the effective state of the active components of the catalyst is accelerated; by introducing metal elements with the ionic radius of more than 0.8nm and less than 0.8nm, such as Cr, Ni, Mg, Mn, Zn, Al and other elements, the catalyst plays a role of structure and electronic assistant, and improves the structure and stability of the catalyst; by introducing rare earth elements, the amount of lattice oxygen of the catalyst is increased, and the catalytic performance of the catalyst is improved; by introducing elements such as Cs, Rb, P, B, Al and the like, the surface modification and the adjustment of the acidity and alkalinity are carried out on the catalyst, and the selectivity and the activity of the catalyst are improved.
The Mo-Bi series catalysts proposed by patents CN1210033A, CN1285238A, CN1294942A and CN1751790A are suitable for being used under the conditions of higher reaction pressure and high propylene load, and can still keep the characteristic of high single yield of acrylonitrile.
Patents CN03151170.8 and CN03151169.4 describe that in the preparation process of catalyst, solid silica with particle size of 5-100 nm is added in 2-25% of silica sol as carrier starting material to improve the performance of catalyst.
In all of the above patent documents, the oxide catalyst is supported on a silica carrier, and in such oxidation catalyst preparation methods, silica sol is used as a source of silica, however, the influencing factor of silica sol is not mentioned in the above patent documents.
Patent CN1129408A proposes that the aluminum content of the silica sol added during the catalyst preparation process is specified, which can significantly improve the selectivity of acrylonitrile, but there is no clear specification on the content of other components.
Patent CN1744949A proposes to control the pore size distribution of the catalyst by changing the primary particle size of the silica raw material.
Catalysts used for ammoxidation of unsaturated olefins generally include an oxide catalyst comprising oxides of molybdenum, bismuth, iron and at least one element selected from the group consisting of potassium, rubidium and cesium, and a silica carrier having the oxide catalyst supported thereon. Through further research, the additive in the carrier is found to have obvious influence on the selectivity and stability of the propylene ammoxidation reaction.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, a catalyst for preparing acrylonitrile by propylene ammoxidation has low selectivity and poor stability, and provides the catalyst for preparing acrylonitrile by propylene ammoxidation, which has the characteristics of high selectivity and good stability.
The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst described in the first technical problem.
The invention also provides a synthesis method for producing acrylonitrile by propylene ammoxidation by adopting the catalyst.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
an acrylonitrile catalyst for ammoxidation process comprising a carrier and an active component comprising the general formula: a. theaBbCcNidFeeBifMo13.6Ox
Wherein A is selected from at least one of K, Rb and Cs; b is at least one selected from Ca, Mn, Co, Mg, Cr, W, P and Nb; c is at least one of rare earth elements; the value range of a is 0.01-2.5; the value range of b is 1-15; the value range of c is 0.01-5; d ranges from 1 to 20; the value range of e is 1-15; the value range of f is 0.01-3; x is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst;
the carrier comprises silicon dioxide and a carrier modifier, and the carrier modifier is selected from at least one of zirconium oxide and titanium oxide.
In the technical scheme, the carrier modifier simultaneously comprises titanium oxide and zirconium oxide, and the titanium oxide and the zirconium oxide have a synergistic effect on the aspects of improving selectivity and stability. The weight ratio of both zirconia and titania is not particularly limited, such as, but not limited to, 1: 1 to 10, and more preferably 1: 1 to 5.
In the above technical solution, the silica is preferably derived from silica sol.
In the above technical scheme, the amount of the carrier is not particularly limited, and is preferably 30 to 70wt% of the weight of the catalyst.
In the technical scheme, the content of the carrier modifier in the carrier is preferably 0.1-5 wt%.
To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the catalyst in one of the above technical problems comprises the following steps:
(a) dissolving at least one salt of the corresponding active component elements except Mo in required amount to obtain a solution I;
(b) mixing silica sol with required amount with a carrier modifier to obtain a mixed solution II;
(c) dissolving molybdenum containing molybdate of a required amount, and mixing the molybdenum containing molybdate with the mixed solution II to obtain mixed solution III;
(d) mixing the solution I and the mixed solution III, and stirring at the pH of 1-7 and the temperature of 20-90 ℃ to obtain slurry I;
(e) and (3) carrying out spray drying and roasting and activating on the slurry I at the temperature of 520-660 ℃ for 0.2-4 hours to obtain the required catalyst.
In the above technical solutions, those skilled in the art can understand that, in the step (b), in order to obtain the uniformly dispersed mixed solution II, the carrier modifier is mixed with the silica sol in the form of fine particles, but the particle size of the carrier modifier particles is not particularly limited, and all the particles can obtain comparable inventive effects. Thus, the effect contemplated by the present invention can be obtained as to whether the silica sol is mixed in the form of a sol of the support modifier or a silica sol is mixed with a powder of the support modifier. When silica sol is mixed with the carrier modifier powder, for example, but not limited to, the particle size of the added carrier modifier powder is 10-200 nm, preferably 10-100 nm, and for the purpose of achieving the same ratio between the examples and the comparative examples, in the specific embodiment of the present invention, the particle size of the carrier modifier is 20 nm.
In the technical scheme, the pH value in the step (d) is preferably 1-5.
In the technical scheme, the temperature of the step (d) is preferably 50-80 ℃.
In the technical scheme, the roasting activation temperature is preferably 550-640 ℃.
In the technical scheme, the roasting activation time is preferably 0.5-2 h.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a process for preparing acrylonitrile by ammoxidizing propylene with ammonia features that under the existance of catalyst, the raw materials of propylene, ammonia and air are reacted to obtain acrylonitrile.
In the above technical solutions, those skilled in the art can reasonably determine the reaction process conditions without creative efforts in light of the present inventive concept.
For example, but not limited to, the reaction process is:
1. raw material molar ratio propylene/ammonia/air 1: 1.05-1.3: 9.2 to 9.8.
2. The reaction temperature is 420-440 ℃.
3. The reaction pressure is 0.06-0.14 MPa.
4. The propylene load WWH of the catalyst is 0.06-0.10 h-1。
The technical key point of the invention is that the selectivity and stability of the catalyst to acrylonitrile are improved by including the carrier modifier in the carrier. The evaluation of the activity of the catalyst according to the invention is carried out in a fluidized-bed reactor having an internal diameter of 38 mm. 400 g of catalyst loading, a reaction temperature of 430 ℃, a molar ratio of air to propylene of 9.7:1, a reaction pressure of 0.085Mpa and a reaction load of 0.06 hours-1The operation is carried out for 1000 hours under the condition, the one-way yield of the acrylonitrile reaches about 83 percent, and a better effect is obtained.
The propylene conversion, acrylonitrile selectivity and once-through yield are defined in the present invention as follows:
the invention is further illustrated by the following examples:
Detailed Description
Comparative example 1
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding 2500 g of silica sol with the weight concentration of 40% to obtain a mixed solution II, mixing the solution I and the mixed solution II, and stirring at the temperature of 80 ℃ under the conditions of pH 5 to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Comparative example 2
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2487 g of 40% silica sol, 8 g of water and 5 g of zirconia were mixed to form a mixture II, wherein the weight concentration of the carrier in the mixture II was 40% and the carrier contained 0.5 wt% of zirconia. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Comparative example 3
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (0)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2425 g of 40% strength silica sol, 45 g of water and 30 g of zirconium oxideMixing to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II is 40%, and the carrier contains 3 wt% of zirconium oxide. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Comparative example 4
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2400 g of 40% silica sol, 60 g of water and 40 g of zirconia were mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II was 40%, and the carrier contained 4 wt% of zirconia. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Comparative example 5
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2487 g of 40% silica sol, 8 g of water and 5 g of titanium oxide were mixed to form a mixture II, wherein the weight concentration of the carrier in the mixture II was 40% and the carrier contained 0.5 wt% of titanium oxide. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Comparative example 6
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2425 g of 40% silica sol, 45 g of water and 30 g of titanium oxide are mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II is 40%, and the carrier contains 3 wt% of titanium oxide. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Comparative example 7
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O、135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2400 g of 40% silica sol, 60 g of water and 40 g of titanium oxide were mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II was 40%, and the carrier contained 4 wt% of titanium oxide. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Example 1
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2425 g of 40% silica sol, 45 g of water, 10 g of zirconia and 20 g of titania are mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II is 40%, and the carrier contains 1 wt% of zirconia and 2 wt% of titania. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Example 2
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2425 g of 40% silica sol, 45 g of water, 15 g of zirconia and 15 g of titania are mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II is 40%, and the carrier contains 1.5 wt% of zirconia and 1.5 wt% of titania. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Example 3
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2425 g of 40% silica sol, 45 g of water, 7.5 g of zirconium oxide and 22.5 g of titanium oxide are mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II is 40%, and the carrier contains 0.75 wt% of zirconium oxide and 22.5 wt% of titanium oxide. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. Spraying the prepared slurryThe microspheres are formed in a dryer and finally calcined in a rotary calcining furnace at 590 ℃ for 2.0 hours to prepare the required catalyst.
Example 4
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2425 g of 40% silica sol, 45 g of water, 6 g of zirconia and 24 g of titania are mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II is 40%, and the carrier contains 0.6 wt% of zirconia and 2.4 wt% of titania. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Example 5
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2425 g of 40% silica sol, 45 g of water, 5 g of zirconia and 25 g of titania are mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II is 40%, and the carrier contains 0.5 wt% of zirconia and 2.5 wt% of titania. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Example 6
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2487 g of 40% strength silica sol, 8 g of water, 1.7 g of zirconium oxide and 3.3 g of titanium oxide were mixed to form a mixture II, wherein the mixture II had a support weight strength of 40% and contained 0.17% by weight of zirconium oxide and 0.33% by weight of titanium oxide. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Example 7
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2450 g of 40% strength silica sol, 30 g of water, 6.7 g of zirconia and 13.3 g of titania are mixed to form a mixed solution II, wherein the weight concentration of the carrier in the mixed solution II is 40%, and the carrier contains 0.67 wt% of zirconia and 1.33 wt% of titania. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
Example 8
111.1 g of Bi (NO)3)3·5H2O, 124.8 g Mn (NO)3)2517.6 g of Ni (NO)3)2·6H2O, 287.6 g Fe (NO)3)3·9H2O, 135.5 g Mg (NO)3)2·6H2O, 3.6 g KOH, 60.7 g Pr (NO)3)3·6H2O and 21.4 g Cr (NO)3)3·9H2The solution I is obtained after the O is dissolved in 160 g of water by heating. 2400 g of 40% silica sol, 60 g of water, 13.3 g of zirconium oxide and 26.7 g of titanium oxide were mixed to form a mixture II, wherein the weight concentration of the carrier in the mixture II was 40%, and the carrier contained 1.33 wt% of zirconium oxide and 2.67 wt% of titanium oxide. 846.0 g (NH)4)6Mo7O24·4H2Dissolving O in 890 g of water, adding the mixed solution II to form a mixed solution III, mixing the solution I and the mixed solution III, and stirring at the pH of 5 and the temperature of 80 ℃ to obtain slurry I. The resulting slurry was subjected to microsphere formation in a spray dryer and finally calcined in a rotary calciner at 590 ℃ for 2.0 hours to produce the desired catalyst.
The catalysts obtained in examples 1 to 8 and comparative examples 1 to 7 were used for the ammoxidation of propylene to acrylonitrile under the following reaction conditions, and the results are shown in Table 1.
The reaction conditions of the above examples and comparative examples were:
phi 38 mm fluidized bed reactor
The reaction temperature is 435 DEG C
The reaction pressure is 0.085MPa
Catalyst loading 400 g
Catalyst propylene load (WWH) 0.06 hours-1
Raw material ratio (mol) C3 ＝/NH31/1.25/9.7
TABLE 1 catalyst composition and evaluation results
Claims (10)
1. An acrylonitrile catalyst for ammoxidation process comprising a carrier and an active component comprising the general formula: a. theaBbCcNidFeeBifMo13.6Ox
Wherein A is selected from at least one of K, Rb and Cs; b is at least one selected from Ca, Mn, Co, Mg, Cr, W, P and Nb; c is at least one of rare earth elements; the value range of a is 0.01-2.5; the value range of b is 1-15; the value range of c is 0.01-5; d ranges from 1 to 20; the value range of e is 1-15; the value range of f is 0.01-3; x is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst;
the carrier comprises silicon dioxide and a carrier modifier, the content of the carrier modifier in the carrier is 0.1-5 wt%, the carrier modifier is zirconia and titania, and the weight ratio of the zirconia to the titania is 1: 1 to 10.
2. The catalyst of claim 1, wherein the weight ratio of zirconia to titania is from 1: 1 to 5.
3. The catalyst of claim 1, wherein the carrier is present in an amount of 30 to 70wt% based on the weight of the catalyst.
4. A method of preparing the catalyst of claim 1, comprising the steps of:
(a) dissolving at least one salt of the corresponding active component elements except Mo in required amount to obtain a solution I;
(b) mixing silica sol with required amount with a carrier modifier to obtain a mixed solution II;
(c) dissolving molybdenum containing molybdate of a required amount, and mixing the molybdenum containing molybdate with the mixed solution II to obtain mixed solution III;
(d) mixing the solution I and the mixed solution III, and stirring at the pH of 1-7 and the temperature of 20-90 ℃ to obtain slurry I;
(e) and (3) spray-drying the slurry I, and roasting and activating the slurry I at 520-660 ℃ for 0.2 ~ 4 h to obtain the required catalyst.
5. The method for preparing a catalyst according to claim 4, wherein the pH in the step (d) is 1 to 5.
6. The method for preparing a catalyst according to claim 4, wherein the temperature in the step (d) is 50 to 80 ℃.
7. The method for preparing a catalyst according to claim 4, wherein the calcination activation temperature is 550 to 640 ℃.
8. The method for preparing the catalyst according to claim 4, wherein the calcination activation time is 0.5 to 2 hours.
9. A process for producing acrylonitrile by ammoxidation of propylene, which comprises reacting propylene, ammonia and air as raw materials in the presence of the catalyst according to claim 1 ~ 3.
10. The method for producing acrylonitrile by propylene ammoxidation according to claim 9, wherein the molar ratio of the raw materials, i.e., propylene/ammonia/air, is = 1: 1.05-1.3: 9.2-9.8, the reaction temperature is 420-440 ℃, the reaction pressure is 0.06-0.14 MPa, and the propylene load WWH of the catalyst is =0.06 ~ 0.10 for 0.10h-1。
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| CN101878194A (en) * | 2007-10-11 | 2010-11-03 | 伊内奥斯美国公司 | Process for the ammoxidation or oxidation of propane and isobutane |
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