CN1101264C - Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation - Google Patents
Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation Download PDFInfo
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- CN1101264C CN1101264C CN99113988A CN99113988A CN1101264C CN 1101264 C CN1101264 C CN 1101264C CN 99113988 A CN99113988 A CN 99113988A CN 99113988 A CN99113988 A CN 99113988A CN 1101264 C CN1101264 C CN 1101264C
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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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Abstract
The present invention relates to a fluid bed catalyst for preparing acrylonitrile from propylene by way of ammoxidation. The fluid bed catalyst contains silicon dioxide carriers and compositions whose chemical formulas are as follows by atomic ratio: AaBbCcGe<d>Na<e>Fe<f>Bi<g>Mo12Ox, wherein A is selected from at least two of Li, K, Rb, Cs, Sm, In or Tl, B is selected from at least one of P, Sb, Cr, W, Pr, Ce, As, B, Te, Cd or V, and C is selected from Ni and Co or the mixture of Ni and Co. The catalyst of the present invention is especially suitable to be used under the conditions of high reaction pressure and high loading capacity of propene, can maintain high single yield of acrylonitrile, and can be used in industrial production.
Description
The present invention relates to fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation.
Vinyl cyanide is important Organic Chemicals, and it is produced by the ammoxidation of propylene reaction.For obtaining the fluid catalyst of high reactivity, highly selective, people have carried out a series of improvement through constantly exploring.These improve and mostly relate to catalyst activity partly, pay attention to the collocation between the catalyst activity component, and improve activity of such catalysts and selectivity, thereby reach the raising of vinyl cyanide once through yield, and the raising of producing load.
Oxidation proceses of ammonia is produced vinyl cyanide through 30 years of development, and the throughput of factory and the market requirement are near balance.The main development tendency of acrylonitrile process has been turned to the transformation of original factory, further to cut down the consumption of raw materials and to increase throughput by the construction new device at present.By transformation to original factory, change the bottleneck in effective catalyst and the elimination production technique, the throughput of vinyl cyanide might improve 50～80%, and required investment only is 20～30% of a new device, economic benefit is very huge.
Can produce two problems during factory transforms: 1. the reaction pressure of fluidized-bed reactor will rise; 2. the loading capacity of catalyzer can not be too many.The catalyzer that for this reason requires to use instead should have higher propylene load and can bear higher reaction pressure.
The reaction pressure of fluidized-bed reactor is to be determined to the resistance drop that absorbs a series of interchanger, tower and pipe arrangement the cat head by reactor outlet.Because the increase of throughput obviously increases the inventory of reactor outlet, above-mentioned resistance drop is increased.In addition, each heat exchanger heat transfer area also need increase heat-exchange equipment inadequately, and resistance drop is further increased.Because environmental requirement, the reactor off-gas that absorbs cat head is forbidden directly to be discharged in the atmosphere, deliver to stove and burn.If like this without induced draft fan, then must improve the absorption tower top pressure.For all the foregoing reasons, the working pressure of reactor will increase by 0.5～1.0 times than design load at present, promptly reaches more than the 0.08MPa.
Above-mentioned second load that problem is a catalyzer, i.e. WWH.Its definition is a catalyzer per ton, per hour can handle what ton propylene.Because the increase of reactor feed amount, if the load of catalyzer is constant, then the catalyzer loading capacity is also wanted corresponding increase.But water-cooled tube insufficient height in the intrinsic fluidized-bed reactor, so the fluid height of catalyst reactor might surpass the height of water-cooled tube.In addition, because the increase of reactor feed amount, so operating linear velocity also significantly improves.The combined influence of these two variations might make reactor dilute phase temperature rise, and causes carbon dioxide production to increase, and the vinyl cyanide selectivity descends.Therefore the WWH of catalyzer is higher can prevent the problems referred to above.
The WWH that improves catalyzer in theory should increase the adsorptive power of catalyzer to propylene, but at present still in the catalyst-free certain element can improve theory to the propylene adsorptive power.The catalyzer of following composition has been proposed in document CN1021638C:
A
aB
bC
cNi
dCo
eNa
fFe
gBi
hM
iMo
jO
x
Wherein A is potassium, rubidium, caesium, samarium, thallium; B is manganese, magnesium, strontium, calcium, barium, lanthanum, rare earth element; C is phosphorus, arsenic, boron, antimony, chromium; M is tungsten, vanadium.
Above-mentioned catalyzer can obtain higher single-pass yield of acrylonitrile, but the propylene of catalyzer load is lower, and single-pass yield of acrylonitrile descends bigger under higher reaction pressure.Studies show that further the B component in the above-mentioned catalyzer is relevant with performance under high pressure to the load of catalyzer with M.Though some element in the B component has effect to improving single-pass yield of acrylonitrile, and the raising of catalyst loading and the performance of high-response pressure are had negative impact, be unfavorable for that catalyzer adapts to elevated pressures, operates under the higher load condition.Once in stipulating in CN1021638C in addition that above-mentioned catalyzer was formed, the summation of i and j is 12, promptly is a constant.Cancel this regulation in the present invention,, will influence single-pass yield of acrylonitrile because molybdenum component will reduce when increasing by this regulation M component.
Introduced a kind of germanic ammoxidation catalyst that obtains the high acrylonitrile yield among document US 5688739 and the US5770757.Adopt molybdenum, bismuth, germanium system in the document, alkali metal containing in the optional elements, but the unexposed example that contains sodium among the embodiment, only disclosing reaction pressure in addition in the document is non-pressurized reaction conditions, not the concrete investigation data under high pressure, high-load condition.
The objective of the invention is to overcome the catalyzer that exists in the above-mentioned document and do not relate to the problem of adaptation, a kind of new fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation is provided than high-response pressure and operational load.This catalyzer can adapt under higher reaction pressure and higher loading condiction to be operated, and keeps high vinyl cyanide once through yield.
The objective of the invention is to realize by following technical scheme: a kind of fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation, form by support of the catalyst with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cGe
dNa
eFe
fBi
gMo
12O
x
A is selected among Li, K, Rb, Cs, Sm, In or the Tl at least two kinds in the formula;
B is selected from least a among P, Sb, Cr, W, Pr, Ce, As, B, Te, Cd or the V;
C is selected from Ni, Co or its mixture;
The span of a is 0.01～1.5;
The span of b is 0.01～3.0;
The span of c is 0.1～12.0;
The span of d is 0.01～2.0;
The span of e is 0.01～0.7;
The span of f is 0.1～8;
The span of g is 0.01～6;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein support of the catalyst is selected from silicon-dioxide, and its consumption is 30～70% by weight percentage.
The value preferable range of c is 2～10 in the technique scheme, and the value preferable range of d is 0.01～1.0, and the value preferable range of e is 0.05～0.5, and the value preferable range of f is 1.0～3.0, and the value preferable range of g is 0.1～2.0.The preferred silicon-dioxide of support of the catalyst, its consumption are 40～60% by weight percentage.
The manufacture method of catalyzer of the present invention there is no particular requirement, can be undertaken by well-established law.At first the catalyzer each component is made solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyzer is made in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyzer of the present invention is:
The molybdenum component is with molybdenum oxide or ammonium molybdate in the catalyzer.
The most handy corresponding acids of phosphorus, arsenic and boron or its ammonium salt in the catalyzer; Tungsten can be with ammonium tungstate or its oxide compound; Vanadium can be used ammonium meta-vanadate; Its oxide compound of germanium; The most handy chromium trioxide of chromium, chromium nitrate or the mixture of the two; Antimony can generate the antimony halides or the antimony colloidal sol of weisspiessglanz with ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, hydrolysis; Other component can maybe can be decomposed into the salt of oxide compound with its nitrate, oxide compound, but preferably uses water miscible nitrate.
Raw material available silicon colloidal sol, silicon gel or both mixtures as carrier silicon-dioxide.If use silicon sol, its quality will meet the requirement of CN1005248C.
It is 47～55% back spraying dryings that the prepared slurry heating is concentrated to solid content.Spray-dryer available pressure formula, two streamings or centrifugal turntable formula, but, can guarantee that the catalyzer of making has good size-grade distribution with centrifugal better.
The roasting of catalyzer can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyzer.The catabolic phase temperature is preferably 200～3002, and the time is 0.5～2 hour.Maturing temperature is 500～800 ℃, is preferably 550～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two stoving ovens, also can be divided into two zones in a stove, also can finish simultaneously in the continous way rotary roasting furnace and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air, prevent that catalyzer is by over reduction.
Adopt the specification of catalyzer manufacturing vinyl cyanide of the present invention required propylene, ammonia and molecular oxygen identical with other ammoxidation catalyst of use.Though the low molecule saturated hydrocarbon content in the raw material propylene to the reaction did not influence, considers that from economic point of view density of propylene is more preferably greater than 85% (mole).Ammonia can be used fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can be used pure oxygen from technical standpoint, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is between 0.8～1.5, is preferably 1.0～1.3.Air and third
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is between 0.8～1.5, is preferably 1.0～1.3.The mol ratio of air and propylene is 8～10.5, is preferably 9.0～9.8.If owing to some operational reason must with higher air than the time, can increase to 11, reaction is not had great effect.But from security consideration, the excess of oxygen in the reactant gases can not preferably be not more than 4% greater than 7% (volume).
When catalyzer of the present invention was used for fluidized-bed reactor, temperature of reaction was 420～470 ℃, was preferably 430～450 ℃.Therefore catalyzer of the present invention is a kind of high pressure, high loading catalyzer of being applicable to, reaction pressure can be more than 0.08MPa in production equipment, for example, and 0.08～0.15MPa.If reaction pressure be lower than 0.08MPa do not have yet any unfavorable shadow to, single-pass yield of acrylonitrile can further improve.
The propylene load (WWH) of catalyzer of the present invention is 0.06～0.15 hour
-1, be preferably 0.07～0.10 hour
-1Loading to hang down not only wastes catalyzer, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.Loading does not too highly have practical significance, because the catalyzer add-on is very few, the heat transfer area that can make catalyst layer internal cooling water pipe causes temperature of reaction uncontrollable less than removing the required area of reaction heat.
The product of making vinyl cyanide with catalyzer of the present invention reclaims process for refining, and available existing production technique need not done any transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, with water at low temperature whole organic products is absorbed again.Absorption liquid is through extractive distillation, dehydrogenation cyanic acid and dewater high-purity propylene nitrile product.
The present invention is by adding component germanium in molybdenum, bismuth, iron and sodium catalyst system, find that this catalyst system has than high-response pressure (0.14MPa), and (WWH is 0.09 hour to higher load
-1) operational capability under the condition, suitably add other effective active components in addition, this catalyzer is operated under elevated pressures, higher load condition, its vinyl cyanide once through yield reaches as high as 82.3%, has obtained effect preferably.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 38 millimeters fluidized-bed reactor.Loaded catalyst 550g, 440 ℃ of temperature of reaction, reaction pressure 0.14MPa, proportioning raw materials (mole) is a propylene: ammonia: air=1: 1.2: 9.8, the propylene load (WWH) of catalyzer is 0.090 hour
-1
Propylene conversion, vinyl cyanide selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment.[embodiment 1]
With 1.8 gram cesium nitrates, 4.64 gram SODIUMNITRATE and 1.87 gram saltpetre mixing, add water 30 grams, the dissolving of heating back gets material (A); 9.34 gram chromium trioxides are dissolved in the 8.4 gram water, get material (B); 395.2 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 325 grams, get material (C); 90.45 gram Bismuth trinitrates, 135.6 are restrained Xiao Suangus, 14.7 gram praseodymium nitrates, 0.97 gram germanium oxide, 298.38 gram nickelous nitrates and 150.8 gram iron nitrates mixing, add water 70 grams, the dissolving of heating back gets material (D).
With material (A) and 1250 gram weight concentration is that 40% silicon sol mixes, under agitation add material (B) and (C) and (D), fully stir slurry, by well-established law the slurry of making is shaped to framboid in spray-dryer, it is 89 millimeters at internal diameter at last, length be in the rotary roasting furnace of 1700 millimeters (89 * 1700 millimeters of φ) in 610 ℃ of roastings 1 hour, the catalyzer of making consists of: 50%Mo
12Bi
1.0Fe
2.0Co
2.5Ni
5.5K
0.1Cs
0.05Cr
0.5Pr
0.3Ge
0.05Na
0.29O
x+ 50%SiO
2[embodiment 2～9 and comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyzer of forming in the following table, and, the results are shown in Table 1 with carrying out the reaction that ammoxidation of propylene generates vinyl cyanide under the prepared catalyzer reaction conditions below.
The reaction conditions of the foregoing description and comparative example is:
38 millimeters fluidized-bed reactors of φ
440 ℃ of temperature of reaction
Reaction pressure 0.14MPa
Loaded catalyst 550g
Catalyzer propylene load (WWH) 0.090 hour
-1
Proportioning raw materials (mole) C
3 =/ NH
3/ air=1/1.2/9.8
Table 1
| Embodiment | Catalyzer is formed | Acrylonitrile yield % | Vinyl cyanide selectivity % | Propylene conversion % |
| Embodiment 1 | Mo 12Bi 1.0Fe 2.0Co 2.5Ni 5.5K 0.1Cs 0.05Cr 0.5Pr 0.3Ge 0.05Na 0.29O x | 80.6 | 81.7 | 98.7 |
| Embodiment 2 | Mo 12Bi 1.0Fe 2.0Co 2.5Ni 5.5K 0.07Cs 0.08Cr 0.8Ge 0.5Na 0.29Sb 0.5O x | 81.4 | 82.1 | 99.2 |
| Embodiment 3 | Mo 12Bi 1.0Fe 2.5Co 1.5Ni 6.0K 0.15Cs 0.05Ge 0.5Na 0.29W 1.0P 0.25O x | 80.0 | 81.2 | 98.5 |
| Embodiment 4 | Mo 12Bi 1.0Fe 1.5Ni 7.0Cs 0.1Pr 0.3Ge 0.2Na 0.29W 0.8Sb 0.5O x | 79.8 | 81.5 | 97.9 |
| Embodiment 5 | Mo 12Bi 1.0Fe 2.0Co 5.0Ni 2.5K 0.05Cs 0.2Cr 0.5Ge 0.5Na 0.29V 0.5P 0.5O x | 81.1 | 82.2 | 98.7 |
| Embodiment 6 | Mo 12Bi 1.0Fe 2.5Co 2.5Ni 6.0K 0.05Cs 0.2Tl 0.05Pr 0.3Ge 0.3Na 0.29Sb 0.5O x | 80.9 | 81.8 | 98.9 |
| Embodiment 7 | Mo 12Bi 1.0Fe 1.5Co 2.5Ni 6.0Cs 0.2Tl 0.25Cr 0.45Pr 0.3Ge 0.03Na 0.29P 0.5O x | 79.5 | 81.0 | 98.1 |
| Embodiment 8 | Mo 12Bi 1.0Fe 2.0Co 2.0Ni 7.0K 0.09Cs 0.05Tl 0.25Ge 0.03Na 0.29W 0.1V 0.3Sb 0.5O x | 82.3 | 82.9 | 99.3 |
| Embodiment 9 | Mo 12Bi 1.0Fe 2.5Co 2.5Ni 6.5K 0.13Cs 0.08Cr 0.5Pr 0.3Ge 0.5Na 0.29W 0.5Sb 0.5O x | 80.7 | 81.5 | 99.0 |
| Comparative example 1 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.17Cs 0.05O x | 76.8 | ||
| Comparative example 2 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.21O x | 76.2 | ||
| Comparative example 3 | Mo 12Bi 0.9Fe 1.8Ni 2.4Co 4.3Na 0.15W 0.45Cr 0.45K 0.15Cs 0.07O x | 77.1 | ||
| Comparative example 4 | Mo 12Bi 0.9Fe 1.8Ni 5.0Mg 2.0Na 0.15W 0.45Cr 0.45Cs 0.09O x | 77.4 |
Claims (7)
1, a kind of fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation, form by support of the catalyst with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cGe
dNa
eFe
fBi
gMo
12O
x
A is selected among Li, K, Rb, Cs, Sm, In or the Tl at least two kinds in the formula;
B is selected from least a among P, Sb, Cr, W, Pr, Ce, As, B, Te, Cd or the V;
C is selected from Ni, Co or its mixture;
The span of a is 0.01～1.5;
The span of b is 0.01～3.0;
The span of c is 0.1～12.0;
The span of d is 0.01～2.0;
The span of e is 0.01～0.7;
The span of f is 0.1～8;
The span of g is 0.01～6;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein support of the catalyst is selected from silicon-dioxide, and its consumption is 30～70% by weight percentage.
2, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that d is 0.01～1.0.
3, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that c is 2～10.
4, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that e is 0.05～0.5.
5, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that f is 1.0～3.0.
6, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, the span that it is characterized in that g is 0.1～2.0.
7, according to the described fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation of claim 1, it is characterized in that support of the catalyst is a silicon-dioxide, its consumption is 40～60% by weight percentage.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113988A CN1101264C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation |
| JP2001518186A JP4095302B2 (en) | 1999-08-19 | 2000-06-21 | Fluidized bed catalyst for the ammoxidation of propylene to acrylonitrile. |
| PCT/CN2000/000167 WO2001014057A1 (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile |
| BRPI0013338-8A BR0013338B1 (en) | 1999-08-19 | 2000-06-21 | fluidized bed catalyst for propylene amoxidation to acrylonitrile. |
| AU53871/00A AU5387100A (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile |
| MXPA02001574A MXPA02001574A (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile. |
| DE10084931.8T DE10084931B3 (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for the ammoxidation of propylene to acrylonitrile |
| ROA200200166A RO120244B1 (en) | 1999-08-19 | 2000-06-21 | Fluidized bed catalyst for ammoxidation of propylene into acrylonitrile |
| US09/642,289 US6420307B1 (en) | 1999-08-19 | 2000-08-18 | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113988A CN1101264C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation |
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| Publication Number | Publication Date |
|---|---|
| CN1285237A CN1285237A (en) | 2001-02-28 |
| CN1101264C true CN1101264C (en) | 2003-02-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113988A Expired - Lifetime CN1101264C (en) | 1999-08-19 | 1999-08-19 | Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408172C (en) * | 2005-01-26 | 2008-08-06 | 中国石油化工股份有限公司 | Acrylonitrile fluid bed catalyst |
| CN100384533C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Catalyst of ammoxidation for propylene |
| CN101279264B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | High load fluidized bed catalyst for preparing acrylonitrile |
| CN109772356B (en) * | 2019-03-07 | 2020-06-02 | 营口市向阳催化剂有限责任公司 | Acrylonitrile catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172693A (en) * | 1996-08-06 | 1998-02-11 | 中国石油化工总公司 | Fluidized bed catalyst for preparing acrylonitrile |
| JPH10156185A (en) * | 1996-08-06 | 1998-06-16 | China Petro Chem Corp | Catalyst for ammoxidation of propylene to acrylonitrile |
| CN1219532A (en) * | 1997-12-11 | 1999-06-16 | 中国石油化工总公司 | Catalyst for propylene and isobutylene ammoxidation fluidized bed |
| JP3058961B2 (en) * | 1991-11-22 | 2000-07-04 | 積水化学工業株式会社 | Exterior wall with eaves attachment means |
| JP3058962B2 (en) * | 1991-11-28 | 2000-07-04 | サンデン株式会社 | Compressor |
-
1999
- 1999-08-19 CN CN99113988A patent/CN1101264C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3058961B2 (en) * | 1991-11-22 | 2000-07-04 | 積水化学工業株式会社 | Exterior wall with eaves attachment means |
| JP3058962B2 (en) * | 1991-11-28 | 2000-07-04 | サンデン株式会社 | Compressor |
| CN1172693A (en) * | 1996-08-06 | 1998-02-11 | 中国石油化工总公司 | Fluidized bed catalyst for preparing acrylonitrile |
| JPH10156185A (en) * | 1996-08-06 | 1998-06-16 | China Petro Chem Corp | Catalyst for ammoxidation of propylene to acrylonitrile |
| CN1219532A (en) * | 1997-12-11 | 1999-06-16 | 中国石油化工总公司 | Catalyst for propylene and isobutylene ammoxidation fluidized bed |
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