CN1939589A - Preparing method of catalyst for preparing unsaturated aldehyde and unsaturated carboxylic acid and preparing method of unsaturated aldehyde and unsaturated carboxylic acid - Google Patents
Preparing method of catalyst for preparing unsaturated aldehyde and unsaturated carboxylic acid and preparing method of unsaturated aldehyde and unsaturated carboxylic acid Download PDFInfo
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Abstract
The present invention provides a method for preparing a catalyzer which is used for preparing unsaturated aldehyde and unsaturated carboxylic acid by employing molecular oxygen to catalyse oxidation of compound selected from propylene, isobutylene and tertbutanol. The catalyzer includes a mixed oxide containing molybdenum, bismuth and iron, wherein a catalyzer precursor is calcined in the gas atmosphere containing molecular oxygen, then implements heat treatment with deoxidize material existing. In addition, the invention provides a method for preparing unsaturated aldehyde and unsaturated carboxylic acid comprising the steps of preparing catalyzer by employing the method, then catalysing oxidating compound selected from propylene, isobutylene and tertbutanol in the gas atmosphere containing molecular oxygen with the catalyzer existing.
Description
Background of invention
1. invention field
The present invention relates to prepare the method for the catalyst that is used to prepare unsaturated aldehyde and unsaturated carboxylic acid.In addition, the invention still further relates to use by the Preparation of Catalyst unsaturated aldehyde of said method acquisition and the method for unsaturated carboxylic acid.
2. description of related art
Be known that for a long time, be used for by utilizing molecular oxygen to prepare methacrylaldehyde and acrylic acid catalyst at the gas phase catalytic oxidation propylene, or be used for by utilizing molecular oxygen to prepare the catalyst of methacrolein and methacrylic acid at the gas phase catalytic oxidation isobutene or the tert-butyl alcohol, the catalyst that comprises the mixed oxide that contains molybdenum, bismuth and iron is effective.This catalyst preparation in accordance with the following methods usually that is used for preparing unsaturated aldehyde and unsaturated carboxylic acid: the dry aqueous solution or aqueous slurry by obtaining at the water mixed material, calcine the catalyst precarsor of gained at last.Calcining is carried out under gas atmosphere that comprises molecular oxygen such as air atmosphere usually, for example as disclosed among JP-A-62-234548, JP-A-4-4048, JP-A-7-124473, JP-A-2000-70719 and the JP-A-2004-351295.
But, the catalytic activity deficiency of catalyst that is used to produce unsaturated aldehyde and unsaturated carboxylic acid of preparation according to conventional methods, therefore, can not be with good conversion ratio propylene oxide, isobutene and the tert-butyl alcohol, and can not obtain corresponding unsaturated aldehyde and unsaturated carboxylic acid with gratifying yield.When the rising reaction temperature when improving conversion ratio, side reaction such as consecutive oxidation take place easily, can not obtain unsaturated aldehyde and unsaturated carboxylic acid with gratifying yield thus.
Therefore, the purpose of this invention is to provide the method that preparation has catalyst superior catalytic activity, that be used to produce unsaturated aldehyde and unsaturated carboxylic acid.In addition, the purpose of this invention is to provide a kind of preparation method, utilize the catalyst that obtains by said method with good conversion ratio propylene oxide, isobutene and the tert-butyl alcohol in the method, thereby prepare corresponding unsaturated aldehyde and unsaturated carboxylic acid with good yield.
Summary of the invention
The invention provides the method for preparing catalyst, described catalyst is used for by preparing unsaturated aldehyde and unsaturated carboxylic acid with molecular oxygen at the compound that the gas phase catalytic oxidation is selected from propylene, isobutene and the tert-butyl alcohol, and described catalyst comprises the mixed oxide that contains molybdenum, bismuth and iron, wherein calcined catalyst precursor under the gas atmosphere of molecule-containing keto; In the presence of reducing substances, heat-treat then.
In addition, the present invention also provides the method for preparing unsaturated aldehyde and unsaturated carboxylic acid, this method comprises following step: utilize the method for preparing catalyst, be selected from the compound of propylene, isobutene and the tert-butyl alcohol then with molecular oxygen catalytic oxidation in gas phase in the presence of this catalyst.
According to the present invention, can make and have catalyst excellent catalytic activity, that be used to prepare unsaturated aldehyde and unsaturated carboxylic acid.And, by using resulting catalyst like this, conversion ratio propylene oxide, isobutene and the tert-butyl alcohol that can be good, thus prepare corresponding unsaturated aldehyde and unsaturated carboxylic acid with good yield.
Detailed Description Of The Invention
To describe the present invention in detail below.In the present invention, the catalyst that is used to prepare unsaturated aldehyde and unsaturated carboxylic acid comprises and contains molybdenum, bismuth and the iron mixed oxide as necessary component.This mixed oxide can comprise the element except that molybdenum, bismuth and iron, preferred nickel and/or cobalt, and the element that is selected from potassium, rubidium, caesium and thallium.
Preferred mixed oxide can be by following general formula (1) example shown:
Mo
aBi
bFe
cA
dB
eC
fD
gO
x (1)
Wherein Mo, Bi and Fe are respectively molybdenum, bismuth and iron; A is nickel and/or cobalt; B is selected from manganese, zinc, calcium, magnesium, tin and plumbous element; C is the element that is selected from phosphorus, boron, arsenic, tellurium, tungsten, antimony, silicon, aluminium, titanium, zirconium and cerium; D is the element that is selected from potassium, rubidium, caesium and thallium; When a=12,0＜b≤10,0＜c≤10,1≤d≤10,0≤e≤10,0≤f≤10 and 0＜g≤2; X is the value that depends on the oxidation state of each element.
In these mixed oxides, the preferred compound (not being with oxygen atom in the example) that uses with following composition.
Mo
aBi
bFe
cCo
dCs
g
(a＝12，0.1≤b≤5，0.5≤c≤5，5≤d≤10，0.01≤g≤1)
Mo
aBi
bFe
cCo
dSb
fK
g
(a＝12，0.1≤b≤5，0.5≤c≤5，5≤d≤10，0.1≤f≤5，0.01≤g≤1)
Mo
aBi
bFe
cNi
dSb
f1Si
f2Tl
g
(a＝12，0.1≤b≤5，0.5≤c≤5，5≤d≤10，0.1≤f1≤5，0.1≤f2≤5，0.01≤g≤1)
About the raw material of above-mentioned catalyst, use the compound that comprises the every kind of element that is contained in the catalyst with the ratio that satisfies aforementioned atomic ratio, as oxide, nitrate, sulfate, carbonate, hydroxide, oxyacid and ammonium salt thereof and halide.For example, about molybdenum compound, can use molybdenum trioxide, molybdic acid, ammonium molybdate etc.; About bismuth compound, can use bismuth oxide, bismuth nitrate, bismuth sulfate etc.; And, can use ferric nitrate (III), ferric sulfate (III), iron chloride (III) etc. about iron compound.
In the method for preparation catalyst of the present invention, will under the gas atmosphere of molecule-containing keto, calcine by the catalyst precarsor of above-mentioned raw materials preparation, in the presence of reducing substances, heat-treat then.Usually can prepare catalyst precarsor in accordance with the following methods: mixed material is to obtain the aqueous solution or aqueous slurry, the dry then aqueous solution or aqueous slurry in water.For example can use drying solution or slurries such as kneader, drying box, Barrate type circulation drying device, spray dryer, flash dryer.
Calcining resulting catalyst precarsor like this under the gas atmosphere of molecule-containing keto.The concentration of molecular oxygen is generally 1～30 volume % in this gas, preferred 10～25 volume %.Usually use air or pure oxygen source, if necessary, use with dilution backs such as nitrogen, carbon dioxide, water, helium, argon gas as molecular oxygen.So resulting gas is as the gas that comprises molecular oxygen.Calcining heat is generally 300～600 ℃, preferred 400～550 ℃.Calcination time is generally 5 minutes～and 40 hours, preferred 1 hour～20 hours.
In the present invention, the catalyst precarsor of the calcining that obtained in the above-mentioned calcining is heat-treated in the presence of reducing substances (hereinafter, this processing be called as reduction sometimes handle).Described reduction is handled can improve activity of such catalysts effectively.
The example of reducing substances can comprise for example hydrogen, ammonia, carbon monoxide, hydrocarbon, alcohol, aldehyde, amine etc.If necessary, these materials use capable of being combined.Preferably, hydrocarbon, alcohol, aldehyde and amine have about 1～about 6 carbon atoms separately.The example of hydrocarbon can comprise saturated aliphatic hydrocarbon such as methane, ethane, propane, normal butane and iso-butane; Aliphatic unsaturated hydrocarbon such as ethene, propylene, alpha-butylene, β-butylene and isobutene; Benzene etc.The example of alcohol can comprise that radical of saturated aliphatic alcohol is as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol; Unsaturated aliphatic alcohol is as allyl alcohol, crotonyl alcohol and metallyl alcohol; Phenol etc.The example of aldehyde can comprise radical of saturated aliphatic aldehyde such as formaldehyde, acetaldehyde, propionic aldehyde, hutanal and isobutylaldehyde; Unsaturated aliphatic aldehyde such as methacrylaldehyde, crotonaldehyde and methacrolein etc.The example of amine can comprise radical of saturated aliphatic amine such as methylamine, dimethylamine, trimethylamine, ethamine, diethylamine and triethylamine; Unsaturated aliphatic amine such as allylamine and diallylamine; Aniline etc.
Usually by reduce processing at the catalyst precarsor that comprises heat treatment calcining under the gas atmosphere of above-mentioned reducing substances.The concentration of reducing substances is generally 0.1～50 volume % in the gas, preferred 1～50 volume %, more preferably 3～30 volume %.Dilution such as available nitrogen, carbon dioxide, water, helium, argon gas reducing substances is so that have above-mentioned concentration.Molecular oxygen can be present in the gas in the scope of not giving reduction processing effect, but does not preferably have molecular oxygen usually.
The temperature that reduction is handled is generally 200～600 ℃, preferred 300～500 ℃.The time of stating former processing is generally 5 minutes～and 20 hours, preferred 30 minutes～10 hours.Preferably the catalyst precarsor by will calcining places container such as tube container or box-type container, makes the gas that contains reducing substances pass this container, reduces processing.In this case, if necessary, the waste gas from container capable of circulation.For example, the catalyst precarsor of calcining is filled in the reaction tube of catalytic gas phase oxidation, makes the gas that contains reducing substances pass this reaction tube,, after this can then carry out catalytic gas phase oxidation to reduce processing.
Usually, the quality of catalyst reduces after reduction is handled, and this may be owing to lose due to the Lattice Oxygen from the catalyst precarsor of calcining.Mass loss is preferably 0.05～6%, and more preferably 0.1～5%.When producing excessive reduction and mass loss when too high, catalytic activity may reduce.In this case, preferably under the gas atmosphere of molecule-containing keto, calcine again, to reduce mass loss.Lose by following equation calculated mass:
Quality * 100 of the catalyst precarsor of calcining are before handled in mass loss (%)=(quality of catalyst after the quality of the catalyst precarsor that reduction is calcined before handling-reduction processing)/reduction
When reducing processing, according to the kind and the heat-treat condition of used reducing substances, reducing substances itself and catabolite thereof can be retained in the catalyst after handling.In this case, the quality of resultant product in the independent measurement catalyst is used the value that obtains by the quality that deducts resultant product the catalyst quality that contains resultant product after reduction the is handled quality as catalyst after handling.Because resultant product is generally carbon, its quality can wait discovery by for example total carbon (TC) measurement.
Usually be needed shape to be used with shaped catalyst.Preferably they are configured as ring, piller (pellets), ball etc. by compressing tablet or extrusion molding.This shaping can be carried out under the state before the calcining under the gas atmosphere of molecule-containing keto, at catalyst precarsor, and can carry out after calcining, perhaps carries out after reduction is handled.In forming process,, can add inorfil that oxidation reaction is basically inertia etc., described in JP-A-9-52053 in order to improve the mechanical strength of catalyst.
The so resulting catalyst that is used to prepare unsaturated aldehyde and unsaturated carboxylic acid has excellent catalytic activity.By the use catalyst, useful molecules oxygen catalytic oxidation propylene in gas phase, thus prepare methacrylaldehyde and acrylic acid with good yield.In addition, by using catalyst, useful molecules oxygen is the catalytic oxidation isobutene or the tert-butyl alcohol in gas phase, thereby prepares methacrolein and methacrylic acid with good yield.
According to the catalytic oxidation in the gas phase, usually catalyst is filled in the fixed bed multitube reaction vessel, comprise molecular oxygen and the initial gas that is selected from the initial compounds of propylene, isobutene and the tert-butyl alcohol to this container supply.Also can use fluid bed and moving bed reaction container.Source of molecular oxygen is generally air, and except initial compounds and molecular oxygen, initial gas can comprise nitrogen, carbon dioxide, carbon monoxide, steam etc.
Reaction temperature is generally 250～400 ℃, and reaction pressure is generally 100～500kPa, but also can under reduced pressure react.The amount of molecular oxygen is generally 1～3 mole of every mole of initial compounds.The space velocity of initial gas (SV) is generally 500～5000/ hours, is benchmark with STP (standard temperature and pressure (STP)).
The specific embodiment
Embodiment
Below embodiments of the invention will be shown, but the invention is not restricted to this.In an embodiment, except as otherwise noted, the ml/min of expression gas flow rate is to be benchmark with STP.
Comparative Examples 1
(a) Preparation of catalysts
With 13,241g ammonium molybdate [(NH
4)
6Mo
7O
244H
2O] be dissolved in 15, in the 000g hot water, be referred to as liquid A.On the other hand, with 6,060g ferric nitrate (III) [Fe (NO
3)
39H
2O], 13,096g cobalt nitrate [Co (NO
3)
26H
2O] and 585g cesium nitrate [CsNO
3] be dissolved in 6, in the 000g hot water, then with 2,910g bismuth nitrate [Bi (NO
3)
35H
2O] be dissolved in wherein, be referred to as liquid B.Agitated liquid A to wherein adding liquid B to obtain slurries, uses the dry slurries of flash dryer to obtain catalyst precarsor then.(by ITM Co., Ltd. makes the silica alumina fiber of adding 6 mass parts, and RFC400-SL), making it to form external diameter then is that 6.3mm, internal diameter are that 2.5mm and length are the ring of 6mm in the catalyst precarsor of 100 mass parts.This ring of calcining 6 hours is to obtain catalyst in 516 ℃ of following air streams.Per 12 molybdenum atoms have 0.96 bismuth atom, 2.4 iron atoms, 7.2 cobalt atoms and 0.48 caesium atom in the catalyst.
(b) oxidation reaction
At internal diameter is in the glass reaction tube of 18mm, fill the catalyst that obtains in the 13ml step (a), be supplied in the pipe simultaneously, under 360 ℃ reaction temperature, carry out oxidation reaction with the flow velocity of 162.5ml/min mist with isobutene/oxygen/nitrogen/steam=1/2.2/6.7/2.1 (mol ratio).The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Embodiment 1
The catalyst that obtains in the 50g Comparative Examples 1 (a) is filled in the glass tube, is supplied in the pipe with the flow velocity of 200ml/min mist simultaneously, under 350 ℃, reduce and handled 5 hours hydrogen/nitrogen=10/90 (volume ratio).Then, stop supplies hydrogen flows down at nitrogen then and makes it to be cooled to room temperature, to obtain reducing the catalyst of handling.The mass loss of being handled the catalyst that causes by reduction is 0.84%.
Carry out and the identical oxidation reaction of Comparative Examples 1 (b), different is to use the catalyst of above acquisition and reaction temperature to become 320 ℃.The result is as shown in table 1.
Embodiment 2
Carry out the step identical with embodiment 1, different is the mist that used gas became hydrogen/nitrogen=20/80 (volume ratio) during reduction was handled, the reduction treatment temperature becomes 400 ℃, and the former processing time become 3 hours, to obtain reducing the catalyst of handling.The mass loss of being handled the catalyst that causes by reduction is 3.52%.
Carry out and the identical oxidation reaction of Comparative Examples 1 (b), different is to use the catalyst of above acquisition and reaction temperature to become 320 ℃.The result is as shown in table 1.
Embodiment 3
Carry out the step identical with embodiment 1, different is the mist that used gas became hydrogen/nitrogen=20/80 (volume ratio) during reduction was handled, and former processing temperature becomes 400 ℃, to obtain reducing the catalyst of handling.The mass loss of being handled the catalyst that causes by reduction is 6.42%.
Then, flow down at the nitrogen of 200ml/min temperature is risen to 200 ℃, in 8 hours, further rise to 400 ℃, under 200ml/min, supply air simultaneously off and on.At 400 ℃ of following stop supplies nitrogen, in 400 ℃ of following air streams, this temperature was kept 1 hour, after reduction is handled, it is cooled to room temperature, to obtain a kind of catalyst of air calcination.The mass loss of catalyst is 0.36% in the summation of loss after the reduction processing and the loss after the air calcination.
Carry out and the identical oxidation reaction of Comparative Examples 1 (b), different is to use the catalyst of above acquisition and reaction temperature to become 320 ℃.The result is as shown in table 1.
Embodiment 4
The catalyst that obtains in the 25g Comparative Examples 1 (a) is filled in the glass tube, is supplied in the pipe with the flow velocity of 600ml/min mist simultaneously, under 366 ℃, reduce and handled 5 hours isobutene/nitrogen/steam=6.8/80.6/12.6 (volume ratio).Stop supplies isobutene and steam flow down at nitrogen then and make it to be cooled to room temperature then, to obtain reducing the catalyst of handling.The mass loss of being handled the catalyst that causes by reduction is 1.18%.
Carry out and the identical oxidation reaction of Comparative Examples 1 (b), different is to use the catalyst of above acquisition and reaction temperature to become 320 ℃.The result is as shown in table 1.
Embodiment 5
Carry out the step identical with embodiment 4, different is to replace isobutene with ethanol, to obtain reducing the catalyst of handling.The mass loss of being handled the catalyst that causes by reduction is 3.11%.
Carry out and the identical oxidation reaction of Comparative Examples 1 (b), different is to use the catalyst of above acquisition and reaction temperature to become 300 ℃.The result is as shown in table 1.
Embodiment 6
The catalyst that obtains in the 25g Comparative Examples 1 (a) is filled in the glass tube, be supplied in the pipe simultaneously, under 366 ℃, reduce and handled 2.5 hours with the flow velocity of 100ml/min mist with methacrolein/nitrogen/steam=4.3/78.2/17.5 (volume ratio).Then, stop supplies methacrolein and steam flow down at nitrogen then and make it to be cooled to room temperature, to obtain reducing the catalyst of handling.The mass loss of being handled the catalyst that causes by reduction is 0.58%.
Carry out and the identical oxidation reaction of Comparative Examples 1 (b), different is to use the catalyst of above acquisition and reaction temperature to become 320 ℃.The result is as shown in table 1.
Table 1
| Reduction is handled | Oxidation reaction | ||||||
| Reducing substances | Temperature (℃) | Time (hour) | Mass loss (%) | Temperature (℃) | Conversion ratio (%) | Yield (%) | |
| Comparative Examples 1 | - | - | - | - | 360 | 99.0 | 76.6 |
| Embodiment 1 | Hydrogen | 350 | 5 | 0.84 | 320 | 99.4 | 79.0 |
| Embodiment 2 | Hydrogen | 600 | 3 | 3.52 | 320 | 99.3 | 77.6 |
| Embodiment 3 | Hydrogen * | 400 * | 5 * | 0.36 * | 320 | 99.1 | 78.1 |
| Embodiment 4 | Isobutene | 366 | 5 | 1.18 | 320 | 99.5 | 77.4 |
| Embodiment 5 | Ethanol | 366 | 5 | 3.11 | 300 | 98.0 | 77.9 |
| Embodiment 6 | Methacrolein | 366 | 2.5 | 0.58 | 320 | 99.3 | 78.0 |
*After reduction is handled, carry out air calcination again.
According to the present invention, provide following invention:
[1] prepares the method for catalyst, described catalyst is used for by preparing unsaturated aldehyde and unsaturated carboxylic acid with molecular oxygen at the compound that the gas phase catalytic oxidation is selected from propylene, isobutene and the tert-butyl alcohol, and described catalyst comprises the mixed oxide that contains molybdenum, bismuth and iron, wherein calcined catalyst precursor under the gas atmosphere of molecule-containing keto; In the presence of reducing substances, heat-treat then.
[2] according to the method for [1], wherein mixed oxide is by shown in the following general formula (1):
Mo
aBi
bFe
cA
dB
eC
fD
gO
x (1)
Wherein Mo, Bi and Fe are respectively molybdenum, bismuth and iron; A is nickel and/or cobalt; B is selected from manganese, zinc, calcium, magnesium, tin and plumbous element; C is the element that is selected from phosphorus, boron, arsenic, tellurium, tungsten, antimony, silicon, aluminium, titanium, zirconium and cerium; D is the element that is selected from potassium, rubidium, caesium and thallium; When a=12,0＜b≤10,0＜c≤10,1≤d≤10,0≤e≤10,0≤f≤10 and 0＜g≤2; X is the value that depends on the oxidation state of each element.
[3] according to the method for [1] or [2], wherein under 300～600 ℃, calcine.
[4] each method in basis [1]～[3] is wherein heat-treated under 200～600 ℃.
[5] each method in basis [1]～[4], wherein the mass loss that is caused by heat treatment is 0.05～6 quality %.
[6] according to each method in [1]～[5], wherein reducing substances be selected from hydrogen, ammonia, carbon monoxide, have 1～6 carbon atom hydrocarbon, have 1～6 carbon atom alcohol, have the aldehyde of 1～6 carbon atom and have the compound of the amine of 1～6 carbon atom.
[7] prepare the method for unsaturated aldehyde and unsaturated carboxylic acid, this method comprises following step: utilize according to each method in [1]～[6] to prepare catalyst, be selected from the compound of propylene, isobutene and the tert-butyl alcohol then with molecular oxygen catalytic oxidation in gas phase in the presence of this catalyst.
Claims (7)
1. method for preparing the catalyst that is used to prepare unsaturated aldehyde and unsaturated carboxylic acid, described unsaturated aldehyde and unsaturated carboxylic acid make by the compound that is selected from propylene, isobutene and the tert-butyl alcohol with molecular oxygen catalytic oxidation in gas phase, and described catalyst comprises the mixed oxide that contains molybdenum, bismuth and iron, wherein calcined catalyst precursor under the gas atmosphere of molecule-containing keto; In the presence of reducing substances, heat-treat then.
2. according to the process of claim 1 wherein that mixed oxide is shown in following general formula (1):
Mo
aBi
bFe
cA
dB
eC
fD
gO
x (1)
Wherein Mo, Bi and Fe are respectively molybdenum, bismuth and iron; A is nickel and/or cobalt; B is selected from manganese, zinc, calcium, magnesium, tin and plumbous element; C is the element that is selected from phosphorus, boron, arsenic, tellurium, tungsten, antimony, silicon, aluminium, titanium, zirconium and cerium; D is the element that is selected from potassium, rubidium, caesium and thallium; When a=12,0＜b≤10,0＜c≤10,1≤d≤10,0≤e≤10,0≤f≤10 and 0＜g≤2; With x be the value that depends on the oxidation state of each element.
3. calcine under 300～600 ℃ according to the process of claim 1 wherein.
4. heat-treat under 200～600 ℃ according to the process of claim 1 wherein.
5. according to the process of claim 1 wherein that the mass loss that is caused by heat treatment is 0.05～6 quality %.
According to the process of claim 1 wherein reducing substances be selected from hydrogen, ammonia, carbon monoxide, have 1～6 carbon atom hydrocarbon, have 1～6 carbon atom alcohol, have the aldehyde of 1～6 carbon atom and have the compound of the amine of 1～6 carbon atom.
7. method for preparing unsaturated aldehyde and unsaturated carboxylic acid, this method comprises following step: utilize to prepare catalyst according to each method in the claim 1～6, be selected from the compound of propylene, isobutene and the tert-butyl alcohol then with molecular oxygen catalytic oxidation in gas phase in the presence of this catalyst.
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|---|---|---|---|
| JP2005286833 | 2005-09-30 | ||
| JP2005286833 | 2005-09-30 | ||
| JP2005312429 | 2005-10-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101579630A (en) * | 2008-05-16 | 2009-11-18 | 住友化学株式会社 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN101579630B (en) * | 2008-05-16 | 2014-04-02 | 住友化学株式会社 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN102137750A (en) * | 2008-07-02 | 2011-07-27 | 巴斯夫欧洲公司 | Method for producing a ring-shaped oxidic molded body |
| CN103721722A (en) * | 2012-10-10 | 2014-04-16 | 上海华谊丙烯酸有限公司 | Composite oxide catalyst and preparation method thereof |
| CN103721722B (en) * | 2012-10-10 | 2017-03-08 | 上海华谊丙烯酸有限公司 | Composite oxide catalysts and preparation method thereof |
| CN103736498A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Propylene oxidation catalyst, preparation method thereof and applications thereof |
| CN103739467A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Method of preparing acraldehyde by propylene oxidation |
| CN103739467B (en) * | 2012-10-17 | 2016-02-10 | 中国石油化工股份有限公司 | Propylene oxidation prepares propenal method |
| CN103736498B (en) * | 2012-10-17 | 2016-04-13 | 中国石油化工股份有限公司 | Propylene oxidation catalyst, preparation method and its usage |
| CN107405609A (en) * | 2015-02-27 | 2017-11-28 | 日本化药株式会社 | For manufacturing the catalyst and its manufacture method and the manufacture method of unsaturated aldehyde and/or unsaturated carboxylic acid of unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN113828325A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Catalyst for preparing acrolein and acrylic acid by propylene oxidation and preparation method thereof |
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