CN1259132C - Fluidized bed catalyst for preparing acrylonitrile by ammoxidation - Google Patents
Fluidized bed catalyst for preparing acrylonitrile by ammoxidation Download PDFInfo
- Publication number
- CN1259132C CN1259132C CNB021452245A CN02145224A CN1259132C CN 1259132 C CN1259132 C CN 1259132C CN B021452245 A CNB021452245 A CN B021452245A CN 02145224 A CN02145224 A CN 02145224A CN 1259132 C CN1259132 C CN 1259132C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acrylonitrile
- present
- span
- ammoxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a fluid bed catalyst for preparing acrylonitrile by propylene ammoxidation. The present invention mainly solves the problems that the powdery catalyst in the prior art has high reaction pressure and high service load. The present invention solves the problems by adopting the technical scheme that the fluid bed catalyst comprises silicon dioxide carriers and a composition with the following chemical formula according to an atomic ratio: Mo12BiaFebNicNrdNaeXfYgOm, wherein X is at least one of Li, K, Rb, Cs, Sm or Tl, and Y is at least one of Co, Mg, Sr, Mn, Ca, Ce, La, B, P, Al or Cr. The present invention is particularly suitable for being used under the condition with a slightly low normal reaction temperature, a low air/propene ratio, a high reaction pressure and a high propene load. High single-pass yield of acrylonitrile can be kept, and the present invention can be used for the industrial production of acrylonitrile.
Description
Technical field
The present invention relates to a kind of fluid catalyst of ammoxidating propylene to prepare acrylonitrile.
Background technology
Acrylonitrile is important Organic Chemicals, and it is produced by the ammoxidation of propylene reaction.For obtaining the fluid catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.These improve and mostly relate to the catalyst activity composition, pay attention to the collocation between the catalyst activity component, and improve activity of such catalysts and selectivity, thereby reach the raising of acrylonitrile once through yield, and the raising of producing load.
Ammonia oxidation is produced acrylonitrile through 40 years of development, and the production capacity of factory and the market demand are near balance.The main development trend of acrylonitrile process is built the technological transformation that new equipment turns to original factory by emphasis, further to cut down the consumption of raw materials and to increase production capacity at present.By transformation to original factory, change the bottleneck in effective catalyst and the elimination production technology, the production capacity of acrylonitrile 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 useful load of catalyst can not be too many.The catalyst that for this reason requires to use instead should be able to move under higher propylene load and higher reaction pressure, and keeps higher acrylonitrile yield.
The reaction pressure of fluidized-bed reactor is to be determined to the resistance drop that absorbs a series of heat exchangers, tower and pipe arrangement the cat head by reactor outlet.Because the increase of production capacity 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 transmission 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 air-introduced machine, then must improve the absorption tower top pressure.For all the foregoing reasons, the operating 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 catalyst, i.e. WWH.Its definition is a catalyst per ton, per hour handles the tonnage of propylene.Under the constant situation of catalyst loading, the reactor feed amount increases, and then the catalyst useful load is also wanted corresponding increase; In addition, the reactor feed amount increases, and causes operating linear velocity also to significantly improve, and bed height increases.The combined influence of these two variations might make reactor dilute phase temperature rise, and causes carbon dioxide production to increase, and the acrylonitrile selectivity descends.Therefore the useful load of catalyst reduces, and WWH is higher can to prevent the problems referred to above, and WWH improves in addition, can obtain higher purpose product output by the unit's of making device in the same time.
High load capacity, high pressure mean that the concentration of reactant propylene, ammonia and oxygen in the reaction atmosphere increases, it requires catalyst must possess the ability of handling more reactants in the unit interval, so the reactivity worth of acrylonitrile catalyst under high load capacity, condition of high voltage, its essence is reflected catalyst activity and optionally the height, the combination property of catalyst itself is had higher requirement.
The WWH that improves catalyst in theory should increase the adsorption activation ability of catalyst to propylene, but at present still in the catalyst-free certain element can improve report to propylene adsorption activation ability.
Introduced the catalyst that a kind of catalyst that uses molybdenum, bismuth, iron, nickel, magnesium, potassium and caesium system carries out preparing acrylonitrile by allylamine oxidation among document US 5093299 and the US5212137.Find out that from embodiment its catalyst system and catalyzing is not contain sodium, though mention thulium cerium and chromium in the optional elements, only use as optional elements.The investigation condition of embodiment is a fixed bed, and 430 ℃ of reaction temperatures are not mentioned reaction pressure concrete in the experimental implementation and operational load situation data.This fixed bed investigation condition is difficult to reflect the truth of fluidized bed process.Introduce in this patent, its catalyst can be operated under lower slightly usually reaction temperature, and it has advantages of high catalytic activity and advantages of excellent oxidation-reduction stability, thereby compares conditional operation applicable to lower air/propylene.
Introduced a kind of ammoxidating propylene to produce acrylonitrile technology in the document US 4228098, catalyst system therefor is to be main active constituent with molybdenum-bismuth-iron-sodium-phosphorus in its technology, its catalyst does not contain the chromium element in forming, when emphasizing that bismuth and iron keep certain proportionate relationship in catalyst, catalyst can have been given play to better comprehensive performance.Disclosed catalyst examination condition is that catalyst propylene load (WWH) is 0.050 hour in the fluidized-bed reactor in this technology
-1, reaction pressure is 0.05MPa, this moment, single-pass yield of acrylonitrile was up to 80.9%, be not disclosed in the examination data of catalyst under high propylene load, the high-response pressure condition, but from disclosed data as can be seen, under the constant situation of other reaction condition, the single-pass yield of acrylonitrile during reaction pressure 0.05MPa is than the examination data under the normal pressure low nearly 5%.There is following shortcoming in the document: lack the data under high propylene load, the high-response pressure condition on the one hand, the production capacity of this sampling device is lower; The once through yield of acrylonitrile is not high yet on the other hand.A kind of acrylonitrile fluidized-bed catalyst of Mo-Bi-Ce-Fe-Co system and the acrylonitrile fluidized-bed catalyst of Mo-Bi-Ce-Fe-Ni system have been introduced among flat 7-289901 of document JP and the flat 7-328441 of JP respectively.Stipulated the corresponding relation of bismuth and cerium in the catalyst component in these two parts of documents, think and use this ammoxidation catalyst composition can not only obtain the acrylonitrile of high yield, even and prolong reaction time in this production process and also can prevent the reduction of acrylonitrile productive rate effectively.Disclosed catalyst examination condition is loaded catalyst 1000～2000 grams, reaction pressure 0.5kg/cm in the fluidized-bed reactor in the document
2, 430～440 ℃ of reaction temperatures, 5～7 seconds times of contact, catalyst propylene load (WWH) is～0.050 hour by calculating as can be known
-1, this moment, single-pass yield of acrylonitrile was up to 82.0%, but they all are not disclosed in the examination data of catalyst under high propylene load, the high-response pressure condition, therefore are difficult to the operating characteristics of this catalyst of explanation under high pressure, high-load condition.Introduced the acrylonitrile catalyst of Mo-Bi-Ce-Fe-Zn system among the flat 7-303836 of document JP.The catalyst examination condition of the document is that internal diameter is 1 centimetre, and reaction pressure is 0.5kg/cm
2, 430 ℃ of reaction temperatures, catalyst reactor loadings are 60 grams, 6.0 seconds times of contact, propylene load (WWH) is 0.042 hour as calculated
-1, this moment, single-pass yield of acrylonitrile was up to 80.0%.Therefore the data that do not relate to high pressure, high load operation condition in the document equally also are difficult to the operating characteristics of this catalyst of explanation under high pressure, high-load condition.
Summary of the invention
Technical problem to be solved by this invention is to overcome the catalyst that exists in the above-mentioned document not relate to problem than high-response pressure and operational load, and a kind of fluid catalyst of new preparing acrylonitrile by ammoxidation is provided.This catalyst can adapt under usually lower slightly reaction temperature, lower air/propylene mol ratio, higher reaction pressure and higher loading condiction to be operated, and keeps high acrylonitrile once through yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of fluid catalyst of preparing acrylonitrile by ammoxidation, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
Mo
12Bi
aFe
bNi
cZr
dNa
eX
fY
gO
m
X is selected from least a among Li, K, Rb or the Cs in the formula;
Y is selected from least a among Co, Mg, Sr, Mn, Ca, Ce, La, B, P, Al or the Cr;
The span of a is 0.1～1.0;
The span of b is 1.0～3.0;
The span of c is 2.5～6.0;
The span of d is 0.001～0.5;
The span of e is 0.01～0.4;
The span of f is 0.01～0.5;
The span of g is 0.1～5.0;
M satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst.
The value preferable range of d is 0.001～0.1 in the technique scheme, and more preferably scope is 0.001～0.05.The value preferable range of g is 1.0～4.5, and the consumption preferable range of carrier silica is 40～60% by weight percentage in the catalyst.
The manufacture method of catalyst of the present invention there is no specific (special) requirements, can be undertaken by well-established law.At first the catalyst each component is made solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyst is made in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyst of the present invention is:
Molybdenum component in the catalyst is with molybdenum oxide or ammonium molybdate.
The most handy corresponding acids of phosphorus in the catalyst and boron or its ammonium salt; The most handy chromium trioxide of chromium, chromic nitrate or the mixture of the two; The most handy its nitrate of all the other components, hydroxide maybe can be decomposed into the salt of oxide.
Raw material available silicon colloidal sol, silicon gel or both mixtures as carrier silica.If use Ludox, its quality will meet the requirement of CN1005248C.
It is 47～55% back spray-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 catalyst of making has good size distribution with centrifugal better.
The roasting of catalyst can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyst.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Sintering 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 roasters, 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,, and prevent that catalyst is by over reduction with generation catalyst activity phase.
Adopt the specification of catalyst manufacturing acrylonitrile 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, and preferable range is 1.0～1.3.The mol ratio of air and propylene is 8～10.5, and preferable range is 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 significant impact.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fluidized-bed reactor, reaction temperature was 420～450 ℃, and preferable range is 425～435 ℃.Catalyst of the present invention is a kind of lower slightly reaction temperature usually that is applicable to, low air/propylene mol ratio, high pressure, high load capacity catalyst, and therefore reaction pressure can be operated under the 0.14MPa condition in process units.Also do not have any adverse effect if reaction pressure is lower than 0.14MPa, single-pass yield of acrylonitrile can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.06～0.15 hour
-1, preferable range is 0.08～0.12 hour
-1Loading to hang down not only wastes catalyst, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.
The product of making acrylonitrile with catalyst of the present invention reclaims process for refining, and available existing production technology 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 gets high-purity propylene nitrile product through extractive distillation after dehydrogenation cyanic acid and the processed.
Because the zirconium in the component is to the regulating catalyst Acidity of Aikalinity, it is favourable to increase lattice vacancy, to improving load, reduce reaction temperature and reducing air/propylene than favourable, and cooperation is formed with the catalyst formulation of optimizing, show that by test catalyst of the present invention can adapt in 425 ℃ lower slightly usually of reaction temperatures, (WWH is 0.11 hour than high-response pressure (0.14MPa), higher load
-1), lower air/propylene mol ratio is condition under to operate at 9.5: 1, and the acrylonitrile once through yield has been up to 80.5% level, obtained better technical effect.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 38 millimeters fluidized-bed reactor.Loaded catalyst 400 grams, 425 ℃ of reaction temperatures, reaction pressure 0.14MPa, raw material proportioning (mole) is a propylene: ammonia: air=1: 1.2: 9.5, the propylene load (WWH) of catalyst is 0.11 hour
-1
Propylene conversion, acrylonitrile selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
2.05 gram cesium nitrates, 3.88 gram sodium nitrate are mixed with 1.75 gram potassium nitrate, add water 30 grams and the dissolving of heating back, obtain material (A); 12.5 gram chromium trioxides are dissolved in the 15 gram water, get material (B); 402.2 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 350 grams, get material (C); 65.0 gram bismuth nitrates, 15.25 gram manganese nitrates, 290.5 gram nickel nitrates, 46.8 gram cerous nitrates, 98.5 gram magnesium nitrates and 175.25 gram ferric nitrates and 2.54 gram zirconyl nitrates are mixed, add water 250 grams, after the heating for dissolving as material (D); Take by weighing phosphoric acid solution 4.35 grams as material (E).
With material (A) and 1280 gram weight concentration is that 40% Ludox mixes, under agitation add material (C), (B), (D) and (E) successively, after fully stirring, get slurry, according to well-established law the slurry of making is carried out the framboid moulding 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 600 ℃ of roastings 2.0 hours, make and consist of:
50％K
0.1Na
0.20Cs
0.065P
0.025Cr
0.35Ce
0.35Ni
6.0Mg
1.25Mn
0.15Zr
0.05Fe
2.0Bi
0.75Mo
12.0O
m+50％SiO
2。
[embodiment 2～5 and comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst of forming in the following table, and under following reaction condition, carry out the reaction that ammoxidation of propylene generates acrylonitrile, the results are shown in Table 1 with prepared catalyst.
The reaction condition of the foregoing description and comparative example is:
38 millimeters fluidized-bed reactors of φ
425 ℃ of reaction temperatures
Reaction pressure 0.14MPa
Loaded catalyst 400 grams
Catalyst propylene load (WWH) 0.11 hour
-1
Raw material proportioning (mole) C
3 =/ NH
3/ air=1/1.2/9.5
Table 1
| Embodiment | Catalyst is formed | Acrylonitrile yield % | Acrylonitrile selectivity % | Propylene conversion % |
| Embodiment 1 | K 0.1Na 0.20Cs 0.065P 0.025Cr 0.35Ce 0.35Ni 6.0Mg 1.25Mn 0.15Zr 0.05Fe 2.0Bi 0.75Mo 12.0O m | 80.0 | 81.5 | 98.1 |
| Embodiment 2 | K 0.1Na 0.20Cs 0.065B 0.02Cr 0.30Ce 0.35Ni 6.0Mg 1.25Mn 0.15Zr 0.1Fe 2.0Bi 0.75Mo 12.0O m | 79.5 | 81.3 | 97.8 |
| Embodiment 3 | K 0.10Na 0.20Cs 0.05B 0.02Cr 0.30La 0.25Ni 6.0Mg 1.25Mn 0.15Zr 0.001Fe 2.0Bi 0.75Mo 12.0O m | 79.7 | 82.0 | 97.2 |
| Embodiment 4 | Li 0.1Na 0.20Cs 0.065P 0.025Cr 0.35Ce 0.40Co 2.5Ni 3.0Mg 1.25Mn 0.15Zr 0.010Fe 2.0Bi 0.75MO 12.0O m | 80.0 | 81.4 | 98.3 |
| Embodiment 5 | K 0.15Na 0.20Rb 0.05P 0.025Cr 0.35Ce 0.35Ni 5.5Mg 1.25Mn 0.20Zr 0.025Fe 2.0Bi 0.75Mo 12.0O m | 80.5 | 81.5 | 98.8 |
| Comparative example 1 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.17Cs 0.05O x | 76.0 | ||
| Comparative example 2 | Mo 12Bi 0.9Fe 1.8Ni 2.4Co 4.3Na 0.15W 0.45Cr 0.45K 0.15Cs 0.07O x | 76.3 | ||
| Comparative example 3 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.21O x | 75.4 | ||
| Comparative example 4 | Mo 12Bi 0.9Fe 1.8Ni 5.0Mg 2.0Na 0.15W 0.45Cr 0.45Cs 0.09O x | 76.7 |
Claims (5)
1, a kind of fluid catalyst of preparing acrylonitrile by ammoxidation, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
Mo
12Bi
aFe
bNi
cZr
dNa
eX
fY
gO
m
X is selected from least a among Li, K, Rb or the Cs in the formula;
Y is selected from least a among Co, Mg, Sr, Mn, Ca, Ce, La, B, P, Al or the Cr;
The span of a is 0.1～1.0;
The span of b is 1.0～3.0;
The span of c is 2.5～6.0;
The span of d is 0.001～0.5;
The span of e is 0.01～0.4;
The span of f is 0.01～0.5;
The span of g is 0.1～5.0;
M satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst.
2, according to the fluid catalyst of the described preparing acrylonitrile by ammoxidation of claim 1, the span that it is characterized in that d is 0.001～0.1.
3, according to the fluid catalyst of the described preparing acrylonitrile by ammoxidation of claim 2, the span that it is characterized in that d is 0.001～0.05.
4, according to the fluid catalyst of the described preparing acrylonitrile by ammoxidation of claim 1, the span that it is characterized in that g is 1.0～4.5.
5, according to the fluid catalyst of the described preparing acrylonitrile by ammoxidation of claim 1, the consumption that it is characterized in that carrier silica in the catalyst is 40～60% by weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021452245A CN1259132C (en) | 2002-11-13 | 2002-11-13 | Fluidized bed catalyst for preparing acrylonitrile by ammoxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021452245A CN1259132C (en) | 2002-11-13 | 2002-11-13 | Fluidized bed catalyst for preparing acrylonitrile by ammoxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1500551A CN1500551A (en) | 2004-06-02 |
| CN1259132C true CN1259132C (en) | 2006-06-14 |
Family
ID=34232319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021452245A Expired - Lifetime CN1259132C (en) | 2002-11-13 | 2002-11-13 | Fluidized bed catalyst for preparing acrylonitrile by ammoxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1259132C (en) |
-
2002
- 2002-11-13 CN CNB021452245A patent/CN1259132C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1500551A (en) | 2004-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1102576C (en) | Fluidized bed catalyst for ammoxidating propylene to prepare acrylonitrile | |
| CN1136980C (en) | Fluidized bed catalyst for ammoxidating propylene to produce acrylonitrile | |
| CN1212187C (en) | Fluidized bed catalyst for preparing acrylonitrile | |
| CN1212185C (en) | Fluidized bed catalyst for preparing acrylonitrile by ammonia oxidation of propene | |
| CN1810364A (en) | Fluid-bed catalyst for ammoxidation to prepare acrylonitrile | |
| CN1107541C (en) | Fluid bed catalyst for acrylonitrile production | |
| CN1810358A (en) | Acrylonitrile fluid bed catalyst | |
| CN1152008C (en) | Fluidized bed catalyst for preparing acrylonitrile by propene ammoxidation | |
| CN1212188C (en) | Fluidized bed catalyst for producing acrylonitrile | |
| CN1099316C (en) | Catalyst for acrylonitrile fluid bed | |
| CN1259132C (en) | Fluidized bed catalyst for preparing acrylonitrile by ammoxidation | |
| CN1157370C (en) | Fluidized bed catalyst for preparing acrylonitrile by propene ammoxidation | |
| CN1152009C (en) | Method for prepn. of fluidized catalyst for prodn. of acrylonitrile | |
| CN1160315C (en) | Fluidized-bed catalyst for preparing acrylonitrile | |
| CN1156439C (en) | Acrylonitrile fluidized-bed catalyst | |
| CN1915499A (en) | Acrylonitrile catalyst in high yield | |
| CN1152010C (en) | Fluidized bed catalyst for preparing acrylonitrile | |
| CN1169783C (en) | Fluidized bed catalyst for preparing acrylonitrile by ammoxidation | |
| CN1160316C (en) | Fluidized-bed catalyst for preparing acrylonitrile by allylamine oxidation | |
| CN1285237A (en) | Fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation | |
| CN1130261C (en) | Propylene ammonoxidizing fluid bed catalyst | |
| CN1285238A (en) | Fluidized bed catalyst for production of acrylonitrile | |
| CN1212186C (en) | Fluidized bed catalyst for producing acrylointrile by ammonia oxidation of propene | |
| CN1810363A (en) | Fluid-bed catalyst for ammoxidation to prepare acrylonitrile | |
| CN1915501A (en) | Catalyst for producing acrylonitrile from ammoxidation of propylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060614 |