CN1033014A - Catalyst containing sodium for acrylonitrile fluidized bed - Google Patents
Catalyst containing sodium for acrylonitrile fluidized bed Download PDFInfo
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- CN1033014A CN1033014A CN 87103455 CN87103455A CN1033014A CN 1033014 A CN1033014 A CN 1033014A CN 87103455 CN87103455 CN 87103455 CN 87103455 A CN87103455 A CN 87103455A CN 1033014 A CN1033014 A CN 1033014A
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Abstract
The invention relates to the catalyzer of ammoxidation of propylene manufactured vinyl cyanide, add an amount of sodium element in the composition, can improve activity of such catalysts and abrasive wear resistance, reduce the loss of catalyzer.It is low that the catalyst containing sodium that uses the present invention to make has temperature of reaction, and catalyst loading is big, active high, and the advantage that selectivity is good can satisfy the requirement that fluidized-bed is produced vinyl cyanide fully.
Description
The present invention is a kind of fluid catalyst that propylene, ammonia and molecular oxygen reaction generate vinyl cyanide that is used for, and has following chemical formula:
In the formula: A is basic metal (K, Rb, Cs) or their mixture; B is dyad (Mn, Mg, Ca, Sr, Ba) or their mixture; C is acid element (P, As, B, Sb, Cr) or their mixture.
A is 0.01-1, and the best is 0.03-0.3; B is 0.1-3, and the best is 0.5-2; C is 0.01-2, and the best is 0.1-1.5; D is 0.01-8, and the best is 0.5-5; E is 0.01-12, and the best is 0.5-8; F is 0.2-0.7, and the best is 0.3-0.5; G is 0.01-8, and the best is 0.1-4; H is 0.01-6, and the best is 0.1-4.
X is the summation that satisfies other element valence requisite oxygen atomicities in the catalyzer.
The invention belongs to the manufacturing of fluid catalyst, it is characterized in that containing in the catalyzer composition of sodium, and as essential element.
Confirm in molybdenum bismuth system catalyst, to add basic metal already and can improve activity of such catalysts and selectivity, but in the catalyzer example that foreign patent provided, the basic metal that the overwhelming majority selects for use is potassium, rubidium and caesium, without sodium.The United States Patent (USP) 3907713(1975 that is delivering for example), 3956181(1976), 3993680(1976), 4123453(1978), 4139552(1979), 4156660(1979), 4162234(1979), 4167494(1979), 4190556(1980), 4192776(1980), 4323703(1982), 4327037(1982), 4377534(1982) and 4397771(1983) in, though mentioning basic metal is a component in the catalyzer, does not all add sodium in its all examples, also not proposing sodium element is the essential component of catalyzer.
It is generally acknowledged that sodium has toxication to molybdenum bismuth system catalyst, so the basic metal in most catalyzer is all without sodium.But study discovery in great detail through us, catalyzer of the present invention contains suitable sodium element, not only can not produce toxication to catalyzer, can improve selectivity of catalyst on the contrary.Supposition is to lose the over oxidation ability owing to sodium ion makes on the catalyst surface some over oxidation active centre be poisoned, and carbon dioxide production is descended, thereby improved selectivity of catalyst.Result of study shows, the introducing of sodium component has also increased the wear resistance of catalyzer.
For example also propose to add the sodium component among Japanese Patent 54-12913 and the 58-2232 in indivedual patents.It is said that the adding of sodium component mainly is to prevent molybdenum component distillation causing loss in the catalyzer.This is that activity is lower, must react under higher temperature of reaction, so the distillation of molybdenum is serious because its catalyzer is formed has obviously differently with the present invention, influences catalyzer work-ing life.Its sodium is with compd B i simultaneously
0.5Na
0.5MoO
4Form is present in the catalyzer, so the content of sodium is higher.
By the data that Japanese Patent 58-2232 example 5 provides, in the small-sized fluidized bed reactor, temperature of reaction is 460 ℃, and the vinyl cyanide once through yield is 80.5%.If the atomic ratio with molybdenum is 12 calculating, then the atomic ratio of sodium is 1.2 in the catalyzer.And catalyzer of the present invention, in diameter is 2 meters large-scale fluidized bed reactor, only 430 ℃ of temperature of reaction, the once through yield of vinyl cyanide can reach more than 81%, and the sodium atom in its catalyzer is 0.4 than only.Because the temperature of reaction of catalyzer of the present invention is very low, need not worry the volatilization of molybdenum.Therefore, adding sodium in the catalyzer of the present invention, mainly is to improve activity of such catalysts and selectivity, rather than solves the volatilization problem of molybdenum.
Catalyzer manufacture method of the present invention can be undertaken by well-established law.At first with each component of catalyzer, carrier and water are mixed into slurry, and the spray-dried microspheroidal that is shaped to adds thermal bake-out at last and makes catalyzer.
The compound method of its slurry can be carried out the aqueous solution and the carrier of each component of catalyzer by the illustrated order of example of the present invention.Also some metallic element and molybdenum compound can be given and be mixed and made into molybdate earlier, mix with other components again.Because catalyzer of the present invention has good wear resistance, it is mentioned need not resemble some patent, carrier is divided add in the catalyzer for several times, has so just simplified manufacturing process.
The used sodium element of catalyzer of the present invention can be used SODIUMNITRATE, sodium hydroxide, and water glass or any sodium compound that can decompose are raw material.Be added to order no standard in the slurry as for the sodium component, can be added to ammonium molybdate solution, in nitrate solution or the ammonia stabilized colloidal silica as carrier.Also can require silicon sol factory to give and earlier the sodium component is added in the ammonia stabilized colloidal silica, but require SiO
2/ Na
2The O weight ratio should be 150-550, and the best is 200-400.
The compound that the available oxide compound of basic metal (potassium, Jia, caesium) maybe can be decomposed into oxide compound is a raw material, the most handy nitrate or oxyhydroxide.
The salt that category-B element in bismuth, iron, cobalt, nickel and the chemical formula, available oxide compound maybe can be decomposed into oxide compound is a raw material.Used salt is preferably water miscible, as nitrate.
C element phosphor in the chemical formula, boron, the most handy corresponding acids of arsenic, also available its ammonium salt.The most handy chromium trioxide of chromium component (sexavalent chrome) or chromium nitrate (trivalent chromium) or its mixture are raw material.Halogenide and antimony colloidal sol that the antimony component can hydrolysis generate weisspiessglanz with antimonous oxide, antimony peroxide are raw material.
Report was once arranged, and the catalyzer of no carrier added(NCA) has very high activity.And the present invention is a kind of catalyzer that is used for fluidized-bed, needs to add a certain proportion of carrier, makes the catalyzer of making have good flowability and suitable physical properties.Catalyzer of the present invention is made up of some special elements simultaneously, therefore still can keep the high reactivity of its catalyzer.
Carrier for catalyzer of the present invention can be used silicon-dioxide, aluminum oxide or alumino silica gel etc., the most handy silicon-dioxide, and adopt silicon sol more convenient as the raw material of silicon-dioxide.Its silicon sol can be used no sodium, the stable silicon sol of ammonia, and dioxide-containing silica is in 40%(weight) about.If, for ease of Preparation of catalysts, wish the sodium component is added in the ammonia stabilized colloidal silica in advance, also can require silicon sol manufactory the requirement of carrier to be produced the silicon sol product of specific standard by the present invention, general dioxide-containing silica is 40% o'clock, and sodium content should be less than 1000PPm.
Prepared slurry need be carried out heat treated.In heat treatment process, the viscosity of slurry, PH, homogeneity, solids content all will change, and help improving spray-dired throughput, can strengthen the homogeneity of catalyst component, improve the abrasive wear resistance of catalyzer.
Slurry after heat treatment promptly carries out spray drying forming.Spray-dryer available pressure formula, two streamings and centrifugal turntable formula etc., but better with the centrifugal turntable formula, can guarantee that the catalyzer of making has good particle size distribution.
The roasting of catalyzer is divided into two stages: each element decomposition of salts and high-temperature roasting in the catalyzer.Its catabolic phase temperature is 200-400 ℃, and the time is 0.5-2 hour, and maturing temperature is 500-800 ℃, preferably 600-700 ℃.Decomposition and roasting are carried out respectively in two stoving ovens, also can divide two stages to carry out in a stoving oven, perhaps will decompose in the continous way rotary roasting furnace with roasting and carry out simultaneously.But in catalyst decomposes and roasting process, noting in the stoving oven to have an amount of airiness.
Adopt catalyzer of the present invention to make the required propylene of vinyl cyanide, the specification of ammonia and molecular oxygen is identical with other catalyzer of use, for example the lower molecular weight saturated hydrocarbon content in the raw material propylene is to the reaction did not influence, but considers from economic point of view, and density of propylene should be greater than the 85%(mole).Ammonia can be used fertilizer grade liquefied ammonia.React required molecular oxygen from the available pure oxygen of technological standpoint, oxygen-rich air, but from economy, resource is convenient considers, and is still more reasonable as source of molecular oxygen with air.
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is stoichiometric ratio 1: 1, and reality can change between 0.8: 1 to 2: 1, but the mole number of ammonia is preferably in 0.9 to 1.3 scope.If the ammonia mol ratio is lower than at 0.9 o'clock, the growing amount of by product propenal can obviously rise, and unfavorable vinyl cyanide reclaims refining.Otherwise, though excess ammonia have no adverse effect for the generation of vinyl cyanide, the oxygen in can consumed cabin air, and make vinyl cyanide reclaim in sulfuric acid consumption rise.
Entering the oxygen of fluidized-bed reactor and the mol ratio of propylene is stoichiometric ratio 1.5: 1, and reality can change between 1: 1 to 4: 1, was preferably between 1.5: 1 to 3: 1.The source of molecular oxygen available air needn't can directly be used " wet air " that contain saturated vapor under atmospheric pressure through dehydrating as previously mentioned.
Add water vapor in the unstripped gas and help improving the selectivity of reaction and improving the vinyl cyanide once through yield, but reduced the throughput of reactor, and also influential slightly to the intensity of catalyzer, for this reason, need not add water vapor during catalyzer of the present invention is raw materials used.As adding water vapor, the mol ratio of its water and propylene is preferably between 0.1: 1 to 3: 1.
Because activity of such catalysts of the present invention is very high, therefore can under lower temperature, react.General temperature of reaction is 400-500 ℃, adopts the temperature of reaction of catalyzer of the present invention can reduce to 380-480 ℃, is preferably 400-450 ℃.
Reaction pressure is relevant with the vinyl cyanide once through yield, the pressure height, and yield descends, and is generally the 1-5 normal atmosphere, is preferably the 1-2 normal atmosphere.
Catalyst loading (WWH) is an important parameter that characterizes catalyst activity.It is defined as:
WWH=propylene feed weight/catalyst weight hours
Because catalyzer of the present invention has very high activity, so the WWH value is bigger, can change in the 0.05-0.25 scope, is preferably 0.06-0.15.
The product recovery process for refining of making vinyl cyanide with catalyzer of the present invention is identical with general method, and promptly the fluidized-bed reactor eluting gas is removed unreacted ammonia through neutralizing tower, and water absorbs whole organism in the absorption tower again.Absorption liquid obtains crude acetonitrile through the desorption tower distillation, obtains the high-purity propylene nitrile through a series of purification operations again.In addition, the desorption tower still water of discharging returns the absorption tower and recycles.
Because catalyzer of the present invention has good selectivity, the growing amount of by product propenal seldom, so polymer concentration is very low in the recirculated water.In the past, polymer concentration can reach 1% in the general recirculated water, polluted very serious to heat exchanger.But polymer concentration only is 0.2-0.3% in the recirculated water of the present invention.Therefore, unnecessary employing such as United States Patent (USP) 4,166,008(1979); 4,334,965(1982) wait the method for polymkeric substance in the reduction recirculated water recommended.
Below be the embodiment of catalyzer of the present invention, wherein transformation efficiency, once through yield and optionally be defined as follows:
Transformation efficiency (%)=(the propylene mole number of reaction)/(propylene feed mole number) * 100
Once through yield (%)=(generating the vinyl cyanide mole number)/(propylene feed mole number) * 100
Selectivity (%)=(generating the vinyl cyanide mole number)/(the propylene mole number of reaction) * 100
(example 1) adds the catalyst containing sodium that sodium is made again by the composition of example 3 in the United States Patent (USP) 3746657.
Produce the stable sodium silicon sol with Shanghai reagent two factories, contain silicon-dioxide 25-27%(weight), contain sodium and be about 5000PPm, remove whole sodium through strong-acid ion exchange resin and obtain sodium-free silica sol, reconcentration is a 40%(weight to dioxide-containing silica) as support material.
With 2.25 gram concentration is that 45% the KOH aqueous solution mixes with 307 gram water, and adding 386 restrains (NH
4)
6Mo
7O
244H
2O stirs and makes its whole dissolvings, gets material (I).
With the silicon-dioxide that 1250 grams are made as stated above, adding 5.52 gram concentration is 40%(weight) the NaOH aqueous solution, stir evenly material (II).
Again with 223 gram Fe(NO
3)
39H
2O, 88.6 gram Bi(NO
3)
35H
2O, 244 gram Co(NO
3)
26H
2O and 134 gram Ni(NO
3)
26H
2O and 66.8 the gram water mixes, heated and stirred make whole dissolve material (III).
At last, material (I), (II), (III) and 10.4 grams, 85% phosphoric acid fully mixed makes slurry, and heating concentrate make that solids content reaches 48%(weight in the slurry), in spray-dryer, carry out drying and moulding by usual method then.Place φ 89 * 1700mm rotary roasting furnace in 670 ℃ of roastings 1 hour at last, the catalyzer of making consists of Na
0.3K
0.1Ni
2.5Co
4.5Fe
3Bi
1P
0.5Mo
12O
X+ 50%SiO
2
It is 38 millimeters fluidized-bed reactor that the catalyzer of making is put into internal diameter, 435 ℃ of temperature of reaction, reaction pressure is a normal pressure, propylene: ammonia: air=1: 1.2: the 10(mole), WWH carries out activity rating 0.045 time, the result is as follows: vinyl cyanide once through yield 79.8%, propylene conversion 96.4%, vinyl cyanide selectivity 82.8%.Catalyst abrasion rate 2.60%.
(comparative example 1) presses the catalyzer of the composition manufacturing of example 3 in the United States Patent (USP) 3746657.
Manufacture method is except not adding the NaOH, and is identical with example 1.The catalyzer of making consists of K
0.1Ni
2.5Co
4.5Fe
3Bi
1P
0.5Mo
12O
X+ 50%SiO
2
Press example 1 similarity condition and investigate activity, the vinyl cyanide once through yield is 77.4%, catalyst abrasion rate 7.92%.
(comparative example 2) presses example 1 composition, and the 40%NaOH5.52 gram is used 14.72 grams instead, uses with quadrat method and makes catalyzer, consists of Na
0.8K
0.1Ni
2.5Co
4.5Fe
3Bi
1P
0.5O
X+ 50%SiO
2Press the condition of example 1 and investigate activity, the vinyl cyanide once through yield 73.9% as a result.
(example 2) prepares catalyzer by the following method.With the 0.94 gram 45%KOH aqueous solution and 2.17 gram 40%NaOH aqueous solution, add 1.75 gram cesium nitrates and 500 grams, 40% ammonia stabilized colloidal silica, as (I).
33.3 the gram Bismuth trinitrate, 28 gram iron nitrates, 91.7 gram Xiao Suangus, 56.4 gram nickelous nitrates, 20 milliliters of dissolvings of mixing and water adding add 22 milliliter of 70% manganese nitrate solution again and mix, as (II).
159 gram ammonium molybdates are added in (I), stir and make its dissolving, add (II) then and mix.Add 3.5 gram chromic trioxides again.Stir, below make catalyzer by example 1 method.It consists of Cs
0.1K
0.1Ni
2.3Co
4.1Fe
0.9Mn
0.9Bi
0.9Cr
0.45Na
0.3Mo
12O
X+ 50%SiO
2By example 1 condition but reactor pressure changes 0.85 kilogram of gauge pressure into, to investigate actively, the vinyl cyanide once through yield is 77.0%.
(comparative example 3) presses the composition of example 2, makes catalyzer but do not add sodium, presses the condition of example 2 and investigates activity, and the vinyl cyanide once through yield is 73.8%, and the wear-resisting intensity of catalyzer is 6.8%.
(comparative example 4) presses the composition of example 2, but do not add sodium and make catalyzer extremely.Press the condition of example 2 and investigate activity, the vinyl cyanide once through yield is 71%.
(example 3) makes following composition catalyzer by example 2 methods:
Cs
0.04K
0.09Ni
2.3Co
4.1Fe
1.8Mn
0.9Bi
0.9Cr
0.45Na
0.3P
0.2Mo
12O
X+SiO
250%。
With 2.1 gram 45%KOH and 5.36 gram 40%NaOH aqueous solution, be added in 1250 grams, the 40% ammonia stabilized colloidal silica, as (I).
33.8 the gram chromium nitrate, 139.3 gram iron nitrates, 82.9 Bismuth trinitrates, 223.8 gram Xiao Suangus, 125.5 gram nickelous nitrates, 46.58 milliliter of 50% manganous nitrate and 16.5 milliliter of 10% cesium nitrate mix, and are (II).
396.9 gram ammonium molybdates are added in (I) stirring and dissolving.Add (II) and 4.9 grams, 85% phosphoric acid again.Below make catalyzer by example 1 method, press example 2 conditions and investigate actively, the vinyl cyanide once through yield is 77.2%.
(example 4) made following catalyzer by example 3 methods and consisted of:
Cs
0.04K
0.09Ni
2.3Co
4.1Fe
1.8Mn
0.7Bi
0.9Cr
0.45Na
0.3P
0.2Mo
12O
X+50%SiO
2。But the add-on of manganous nitrate changes 42.57 milliliters into, and replaces chromium nitrate with 8.63 gram chromic trioxides.Press example 2 conditions and investigate activity, the vinyl cyanide once through yield is 77.7%.
(example 5) makes the catalyzer of following composition:
Cs
0.05K
0.1Ni
2.5Co
4.5Fe
2Mn
1Bi
1Cr
0.5Na
0.4Mo
12O
X+ 50%SiO
2Catalyzer.
Carrier is with 40% ammonia stabilized colloidal silica, and requires manufactory to regulate wherein sodium content to 1100PPm, as the raw material of making catalyzer.
15.3 gram ammonium molybdates are dissolved in 50 ml waters, and 83.2 gram Bismuth trinitrates are dissolved in 100 milliliters of 1: 1 nitric acid.Both mix a kind of solution, be (I).
139.8 the gram iron nitrate, 224.6 Xiao Suangus, 125.9 gram nickelous nitrates, 46.7 milliliter of 50% manganous nitrate, 16.9 milliliter of 10% cesium nitrate and 8.7 gram chromic trioxides mix, and add 60 ml waters and make it dissolving, are (II).
351.3 the gram ammonium molybdate is dissolved in 300 ml waters, adds 1250 gram above-mentioned raw materials silicon sol.Add 2.1 gram 45%KOH, (I) liquid and (II) liquid again.Below make catalyzer by the method for example 1.
Press the condition of example 2 and investigate activity, the vinyl cyanide once through yield is 75.4%.
(example 6) makes the catalyzer of following composition
Cs
0.1K
0.2Ni
2.5Co
4.5Fe
2Mn
1Bi
1Cr
0.5Na
0.4Mo
12O
X+50%SiO
2。
45.3 gram ammonium molybdates are dissolved in 530 milliliters of hot water, and 83.2 gram Bismuth trinitrates are dissolved in the solution of 29 milliliters of concentrated nitric acids and 230 ml waters.Both mix, and regulating PH with ammoniacal liquor is 2.8, get a kind of white precipitate, are (I).
139.8 the gram iron nitrate, 224.6 gram Xiao Suangus, 125.9 gram nickelous nitrates, 46.7 milliliter of 50% manganous nitrate, 33.8 milliliter of 10% cesium nitrate and 33.8 gram chromium nitrates mix, and add 50 ml waters and make it dissolving, are (II).
321.3 the gram ammonium molybdate is dissolved in 300 ml waters, adds the raw silicon colloidal sol of 1250 gram examples 5, adds 4.2 gram 45%KOH solution again and mixes.Add (I) suspension and (II) later on respectively and make slurry.Below make catalyzer by the method for example 1.Press the condition of example 2 and investigate activity, the vinyl cyanide once through yield is 76.9%.
(example 7) pressed the method for example 6 and made catalyzer, but with 44.4 gram magnesium nitrates replacements manganous nitrate wherein, catalyzer consists of: Cs
0.1K
0.2Ni
2.5Co
4.5Fe
2Mg
1Bi
1Cr
0.5Na
0.4Mo
12O
X+ 50%SiO
2Press the condition of example 2 and investigate activity, the vinyl cyanide once through yield is 75.1%.
(example 8) pressed the method for example 6 and made catalyzer, but with 40.9 nitrocalcite replacement manganous nitrate wherein, catalyzer consists of:
Cs
0.1K
0.2Ni
2.5Co
4.5Fe
2Ca
1Bi
1Cr
0.5Na
0.4Mo
12O
X+50%SiO
2。Press the condition of example 2 and investigate activity, vinyl cyanide once through yield 74.7%.
(example 9) makes catalyzer with the method for example 6, investigates its activity in 2 meters of diameters large-scale fluidized bed.Temperature of reaction 425-430 ℃, reaction pressure 0.5kg/cm
2(table), linear speed 0.58 meter per second, WWH0.085, propylene: ammonia: air=1: 1.15: the 10.6(mol ratio).
Mean value as a result in 30 days is as follows:
Vinyl cyanide once through yield 82.1%, propylene conversion 99.8%, vinyl cyanide selectivity 82.3%.
The by product once through yield: acetonitrile is 3.6%, HCN5.1%, CO
27.5%, CO1.2%, propenal 0.3%.
Above result shows that catalyst containing sodium of the present invention has high activity and selectivity.
" catalyst containing sodium for acrylonitrile fluidized bed " errata
Claims (3)
1, a kind of fluid catalyst that is used for propylene, ammonia and molecular oxygen reaction generation vinyl cyanide has following chemical formula:
In the formula: A is basic metal (K, Rb, Cs) or their mixture; B is divalent metal element (Mn, Mg, Ca, Sr, Ba) or their mixture; C is acid element (P, As, B, Sb, Cr) or their mixture.
A is 0.01-1, and the best is 0.03-0.3; B is 0.1-3, and the best is 0.5-2; C is 0.01-2, and the best is 0.1-1.5; D is 0.01-8, and the best is 0.5-5; E is 0.01-12, and the best is 0.5-8; G is 0.01-8, and the best is 0.1-4; H is 0.01-6, and the best is 0.1-4.X is the summation that satisfies other element valence requisite oxygen atomicity in the catalyzer.
It is characterized in that having introduced in the catalyzer sodium component, sodium atom is 0.2-0.7 than (f), and the sodium component of introducing can be a raw material with SODIUMNITRATE, sodium hydroxide, water glass or any decomposable sodium compound.The sodium component can be added to ammonium molybdate solution, in nitrate solution or the ammonia stabilized colloidal silica as carrier.Also can require silicon sol factory in advance the sodium component to be added in the ammonia stabilized colloidal silica, but must keep the SiO of ammonia stabilized colloidal silica
2/ Na
2The O weight ratio is 150-550.
2,, it is characterized in that sodium atom is than (f) the best 0.3-0.5 of being in the catalyzer according to right 1 described catalyzer.
3,, it is characterized in that the sodium component is added in the ammonia stabilized colloidal silica SiO that it is best according to the described catalyzer of claim 1
2/ Na
2The O weight ratio is 200-400.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103455.7A CN1005248B (en) | 1987-05-14 | 1987-05-14 | Acrylonitrile fluidized bed sodium-containing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103455.7A CN1005248B (en) | 1987-05-14 | 1987-05-14 | Acrylonitrile fluidized bed sodium-containing catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1033014A true CN1033014A (en) | 1989-05-24 |
| CN1005248B CN1005248B (en) | 1989-09-27 |
Family
ID=4814439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87103455.7A Expired CN1005248B (en) | 1987-05-14 | 1987-05-14 | Acrylonitrile fluidized bed sodium-containing catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840648A (en) * | 1997-09-02 | 1998-11-24 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
| CN1081488C (en) * | 1998-03-30 | 2002-03-27 | 中国石油化工总公司 | Catalyst for ammonoxidating propylene to produce acrylonitrile |
| CN1086152C (en) * | 1997-09-03 | 2002-06-12 | 中国石油化工总公司 | Production of propylene by ammoxidation of olefins |
| CN101524645B (en) * | 2008-03-03 | 2013-04-10 | 大野绿水株式会社 | Catalyst for producing acrylonitrile and process for producing acrlyonitrile |
| CN105664962A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Catalyst for preparing acrylonitrile from propylene by ammoxidation |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279265B (en) * | 2007-04-04 | 2010-12-22 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing acrylonitrile |
-
1987
- 1987-05-14 CN CN87103455.7A patent/CN1005248B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840648A (en) * | 1997-09-02 | 1998-11-24 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
| CN1086152C (en) * | 1997-09-03 | 2002-06-12 | 中国石油化工总公司 | Production of propylene by ammoxidation of olefins |
| CN1081488C (en) * | 1998-03-30 | 2002-03-27 | 中国石油化工总公司 | Catalyst for ammonoxidating propylene to produce acrylonitrile |
| CN101524645B (en) * | 2008-03-03 | 2013-04-10 | 大野绿水株式会社 | Catalyst for producing acrylonitrile and process for producing acrlyonitrile |
| CN105664962A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Catalyst for preparing acrylonitrile from propylene by ammoxidation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005248B (en) | 1989-09-27 |
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