CN105664962A - Catalyst for preparing acrylonitrile from propylene by ammoxidation - Google Patents
Catalyst for preparing acrylonitrile from propylene by ammoxidation Download PDFInfo
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Abstract
The present invention relates to a catalyst for preparing acrylonitrile from propylene by ammoxidation and a preparation method and application thereof, and mainly solves the problem of low yield of acrylonitrile in the prior art. The catalyst for preparing acrylonitrile from propylene by ammoxidation well solves the problems, the catalyst for preparing acrylonitrile from propylene by ammoxidation comprises a silica-sol-derived silica carrier and an active ingredient represented by formula AaBbCcBidMo13.6Ox; wherein A is selected from at least one of K, Rb and Cs; B is selected from at least one of Ca, Mn, Fe, Co, Ni, Mg, Cr, W, P and Nb; C is selected from at least one of rare earth elements; the amount of the carrier accounts for 30-70wt% of the weight of the catalyst, and the content of sodium in silica sol is 0.02 *10<-2>-0.4* 10<-2> calculated on the basis of a molar ratio of sodium to silicon atoms, and the catalyst can be used for preparing acrylonitrile from propylene by ammoxidation in industrial production.
Description
Technical field
The present invention relates to the Catalysts and its preparation method of a kind of ammoxidating propylene to prepare acrylonitrile, and produce the method for vinyl cyanide.
Background technology
The industrial production that current olefin ammoxidation prepares unsaturated nitrile still generally adopts fluidized-bed ammonia oxidation process, and catalyzer as one of the core technology of this technique, its research, improves and paid attention to always. The catalyzer of current industrial ammoxidating propylene to prepare acrylonitrile mainly contains two classes: Mo-Bi system and Sb system, and wherein Mo-Bi series catalysts is occupied an leading position, and reaches the 95% of olefin oxidation market, and forefathers' research and exploration also mainly concentrate on Mo-Bi series catalysts. The metal component having variable valence state by introducing in the catalyst improves the oxidation-reduction performance of catalyzer such as elements such as Fe, Ce, accelerates to recover the significant condition of catalyst activity component; It is greater than 0.8nm by introducing ionic radius and it is less than the metallic element of 0.8nm, such as elements such as Cr, Ni, Mg, Mn, Zn, Al, play structure and electronic auxiliary effect, improve the Structure and stability energy of catalyzer; By introducing rare earth element, it is to increase the lattice oxygen quantity of catalyzer, improve the catalytic performance of catalyzer; By introducing the elements such as Cs, Rb, P, B, Al, catalyzer is carried out the adjustment of finishing and acid-basicity, improves selectivity of catalyst and activity.
The Mo-Bi series catalysts that patent CN1210033A, CN1285238A, CN1294942A, CN1751790A propose uses when being applicable to higher reaction pressure and high propylene load, still can keep the feature of very high single-pass yield of acrylonitrile.
Patent CN03151170.8 and CN03151169.4 describes in catalyst preparation process, and the grain diameter adding 2～25% in carrier initiator silicon sol is that the solid silica of 5～100 nanometers is to improve catalyst performance.
In patent documentations all above, oxide catalyst is loaded on a kind of silica supports, and in such oxide catalyst preparation method, all use silicon sol as the source of silicon-dioxide, but the influence factor of silicon sol is not all mentioned in above patent documentation.
The aluminium content of the silicon sol that patent CN1129408A proposition adds in catalyst preparation process specifies, it is possible to improves the selectivity of vinyl cyanide significantly, but the content of other components is not had clear stipulaties.
Patent CN1744949A proposes the initial particle by changing silica material and the hole degree distribution of catalyzer is controlled.
But the receipts rate of vinyl cyanide awaits further raising in prior art.
Summary of the invention
One of technical problem to be solved by this invention is the problem that in prior art, acrylonitrile yield is low, it is provided that the catalyzer of a kind of ammoxidating propylene to prepare acrylonitrile, and this catalyzer has the high feature of acrylonitrile yield.
The two of technical problem to be solved by this invention are to provide the preparation method of one of a kind of above-mentioned technical problem described catalyzer.
The three of technical problem to be solved by this invention are the methods of the ammoxidating propylene to produce acrylonitrile adopting one of above-mentioned technical problem described catalyzer.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: for the catalyzer of ammoxidating propylene to prepare acrylonitrile, taking the silicon-dioxide in silicon sol source as carrier, and the active ingredient containing following general formula represents: AaBbCcBidMo13.6Ox;
At least one that in formula, A is selected from K, Rb and Cs; B is selected from least one in Ca, Mn, Fe, Co, Ni, Mg, Cr, W, P and Nb; C is selected from least one in rare earth element; The span of a is 0.01～2.5; The span of b is 1～15; The span of c is 0.01～5; The span of d is 0.01～3; X is the Sauerstoffatom sum met in catalyzer needed for each element valence, and the consumption of carrier is 30～70wt% of catalyst weight, wherein in silicon sol sodium content taking the molar ratio computing of relative Siliciumatom as 0.02 × 10-2～0.4 × 10-2。
In technique scheme, in loaded catalyst, vector contg is preferably 40～60wt%.
In technique scheme in silicon sol sodium content with the molar ratio computing of relative Siliciumatom, it is preferable to 0.04 × 10-2～0.22 × 10-2; More preferably 0.045 × 10-2～0.12 × 10-2; Most preferably 0.045 × 10-2～0.063 × 10-2。
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of the described catalyzer of one of above-mentioned technical problem, comprises the following steps:
A (), by the compound dissolution of A, B, C and Bi of institute's requirement, obtains solution I;
B molybdate containing institute's requirement molybdenum is dissolved by (), and mix with silicon sol, obtains solution II;
C solution I and II are mixed by (), stir at 20～90 DEG C, obtain the slurry I that pH is 1～7;
D () slurry I is spray-dried and calcination activation 0.2～4 hour must required catalyzer at 520～660 DEG C.
In technique scheme, the pH of slurry 1 is preferably 1～5.
In technique scheme, the temperature that step (c) stirs is preferably 50～80 DEG C.
In technique scheme, the temperature of calcination activation is preferably 550～640 DEG C, and the time of calcination activation is preferably 0.5～2h.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the method for ammoxidating propylene to produce acrylonitrile, taking propylene, ammonia and air as raw material, material molar ratio propylene/ammonia/air=1/1.05～1.3/9.2～9.8, reaction conditions is: temperature of reaction 420～440 DEG C, reaction pressure is 0.06～0.14MPa, the propylene load WWH=0.06～0.10h of catalyzer-1。
The technology of the present invention is it is crucial that by controlling sodium content in the silicon sol added in catalyst preparation process, thus realizes the high acrylonitrile receipts rate of ammoxidation of propylene reaction.
The active examination of catalyzer of the present invention be internal diameter be 38 millimeters fluidized-bed reactor in carry out. Loaded catalyst 400 grams is 430 DEG C, C in temperature of reaction3 =/NH3/ air (mol ratio)=1/1.25/9.7, reaction pressure is 0.085Mpa, and reaction load is (WWH) 0.06 hour-1When operate 1000h, vinyl cyanide once through yield reaches about 83%, obtains good effect.
Propylene conversion, vinyl cyanide selectivity and once through yield are defined as follows in the present invention:
Below by specification drawings and specific embodiments, the present invention is further elaborated:
Accompanying drawing illustrates:
Fig. 1 is comparative example 1～5 and Na content and acrylonitrile yield corresponding relation curve in the catalyzer of embodiment 1～6 in embodiment.
Can visually see from Fig. 1, when sodium content in silicon sol is taking the molar ratio computing of relative Siliciumatom as 0.02 × 10-2～0.4 × 10-2Time, there is peak value in acrylonitrile yield.
Embodiment
Comparative example 1
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.005 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Comparative example 2
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.011 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Comparative example 3
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.016 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Comparative example 4
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.5 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Comparative example 5
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I.846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 1.4 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 1
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.025 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 2
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.045 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 3
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.056 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 4
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.063 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 5
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I.846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.12 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 6
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.22 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 7
After 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.056 × 10 that 2000 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 8
By 111.1 grams of Bismuth trinitrates, 124.8 grams of manganous nitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, after 3.6 grams of potassium hydroxide, 60.7 grams of praseodymium nitrates and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.056 × 10 that 1500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 9
After 111.1 grams of Bismuth trinitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 15.6 grams of potassium hydroxide and 21.4 grams of chromium nitrate heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.056 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 10
After 111.1 grams of Bismuth trinitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 135.5 grams of magnesium nitrates, 15.6 grams of potassium hydroxide heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water, and adds the silicon sol (sodium content 0.056 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I.The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Embodiment 11
After 111.1 grams of Bismuth trinitrates, 517.6 grams of nickelous nitrates, 287.6 grams of iron nitrates, 271.0 grams of magnesium nitrates, 15.6 grams of potassium hydroxide heating for dissolving, obtain solution I. 846.0 grams of ammonium molybdates are dissolved in quantitative water and dissolve, and add the silicon sol (sodium content 0.056 × 10 that 2500 gram weight concentration are 40%-2), obtaining solution II, solution I and solution II are mixed, be 5 at pH, temperature is stir under 80 DEG C of conditions, obtains slurry I. The slurry made is carried out framboid in spray-dryer shaping, finally in 590 DEG C of roastings 2.0 hours in rotary roasting furnace, obtained required catalyzer.
Catalyzer obtained in embodiment 1～11 and comparative example 1～5 carries out the reaction that ammoxidation of propylene generates vinyl cyanide under following reaction conditions, the results are shown in Table 1.
The comparison diagram that catalyzer obtained in embodiment 1～6 and comparative example 1～5 carries out sodium content in the reacted acrylonitrile yield of ammoxidation of propylene and catalyzer under following reaction conditions is shown in Fig. 1.
Table 1 catalyzer composition and evaluation result
Claims (9)
1. for the catalyzer of ammoxidating propylene to prepare acrylonitrile, taking the silicon-dioxide in silicon sol source as carrier, the active ingredient containing following general formula represents: AaBbCcBidMo13.6Ox;
At least one that in formula, A is selected from K, Rb and Cs; B is selected from least one in Ca, Mn, Fe, Co, Ni, Mg, Cr, W, P and Nb; C is selected from least one in rare earth element; The span of a is 0.01～2.5; The span of b is 1～15; The span of c is 0.01～5; The span of d is 0.01～3; X is the Sauerstoffatom sum met in catalyzer needed for each element valence, and the consumption of carrier is 30～70wt% of catalyst weight, wherein in silicon sol sodium content taking the molar ratio computing of relative Siliciumatom as 0.02 × 10-2～0.4 × 10-2。
2. catalyzer according to claim 1, it is characterised in that the consumption of carrier is 40～60wt% of catalyst weight.
3. catalyzer according to claim 1, it is characterised in that in silicon sol, sodium content is taking the molar ratio computing of relative Siliciumatom as 0.04 × 10-2～0.22 × 10-2。
4. the preparation method of catalyzer according to claim 1, comprises the following steps:
A (), by the compound dissolution of A, B, C and Bi of institute's requirement, obtains solution I;
B molybdate containing institute's requirement molybdenum is dissolved by (), and mix with silicon sol, obtains solution II;
C solution I and II are mixed by (), stir at 20～90 DEG C, obtain the slurry I that pH is 1～7;
D () slurry I is spray-dried and calcination activation 0.2～4 hour must required catalyzer at 520～660 DEG C.
5. the preparation method of catalyzer according to claim 4, it is characterised in that the pH of slurry 1 is 1～5.
6. the preparation method of catalyzer according to claim 4, it is characterised in that the temperature that step (c) stirs is 50～80 DEG C.
7. the preparation method of catalyzer according to claim 4, it is characterised in that calcination activation temperature is 550～640 DEG C.
8. the preparation method of catalyzer according to claim 4, it is characterised in that the calcination activation time of catalyzer is 0.5～2h.
9. the method for ammoxidating propylene to produce acrylonitrile, it is characterized in that taking propylene, ammonia and air as raw material, material molar ratio propylene/ammonia/air=1/1.05～1.3/9.2～9.8, reaction conditions is: temperature of reaction 420～440 DEG C, reaction pressure is 0.06～0.14MPa, the propylene load WWH=0.06～0.10h of catalyzer-1。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113332993A (en) * | 2021-06-19 | 2021-09-03 | 营口风光新材料股份有限公司 | Catalyst for preparing acrylonitrile by propylene ammoxidation and preparation method and application thereof |
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| CN103657669A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing unsaturation nitrile through ammoxidation and method thereof |
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| CN103418405A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Replenishment catalyst for maintaining stabilization production of acrylonitrile device |
| CN103657669A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing unsaturation nitrile through ammoxidation and method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113332993A (en) * | 2021-06-19 | 2021-09-03 | 营口风光新材料股份有限公司 | Catalyst for preparing acrylonitrile by propylene ammoxidation and preparation method and application thereof |
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Application publication date: 20160615 |