CN101269333A - Method for preparing unsaturated aldehyde and/or unsaturated carboxylic acid - Google Patents
Method for preparing unsaturated aldehyde and/or unsaturated carboxylic acid Download PDFInfo
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- CN101269333A CN101269333A CNA2008100830666A CN200810083066A CN101269333A CN 101269333 A CN101269333 A CN 101269333A CN A2008100830666 A CNA2008100830666 A CN A2008100830666A CN 200810083066 A CN200810083066 A CN 200810083066A CN 101269333 A CN101269333 A CN 101269333A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
- B01J2523/15—Caesium
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
- B01J2523/53—Antimony
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
- B01J2523/54—Bismuth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
- B01J2523/68—Molybdenum
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/845—Cobalt
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Abstract
Unsaturated aldehyde and/or unsaturated carboxylic acid are produced with excellent transform rate and satisfactory yield rate by catalysis gas phase oxidization of at least one compound selected from the group consisting of propylene, isobutylene and tert-butyl alcohol. Two or more sorts of catalysts composed by special mixed oxides whose types of ingredients forming metals and proportion of content are different, are filled into a reaction pipe, thereby enhancing catalysis activity from an inlet of feeding gas to an outlet of feeding gas, then the feeding gas is fed into the reaction pipe, and wherein the catalysts are obtained by the following steps of: drying water solution or water suspension comprising all kinds of catalyst ingredients, afterwards, calcining the water solution or water suspension in an ambience with the gas comprising molecular oxygen, then performing heat treatment in presence of deoxidized substances.
Description
Invention field
The present invention relates to a kind of method that is used to produce the unsaturated aldehyde unsaturated carboxylic acid, comprise that the feeding gas and the molecular oxygen that will contain at least a compound that is selected from propylene, isobutene and the tert-butyl alcohol are fed in the reaction tube, with described at least a compound in gas phase catalytic oxidation to obtain unsaturated aldehyde and/or unsaturated carboxylic acid.
The description of association area
An example as the method that is used to produce unsaturated aldehyde and/or unsaturated carboxylic acid, advised a kind of method, comprise to contain and be selected from propylene, the feeding gas of at least a compound of the isobutene and the tert-butyl alcohol and molecular oxygen are fed in the reaction tube, with with at least a compound catalytic oxidation in gas phase, wherein after the kind of the metal ingredient by change constituting catalyst and quantity prepare multiple catalyst with different catalytically active, these catalyst are filled in the reaction tube, increase from the feeding gas feeding gas outlet catalyst activity that enters the mouth thus, and feeding gas is fed in the reaction tube (referring to U.S. Patent number 5,276,178 and JP-A-2000-351744).
Yet this conventional method is at the conversion ratio of propylene, isobutene or the tert-butyl alcohol or may not be gratifying aspect unsaturated aldehyde and/or the unsaturated carboxylic acid yield.
Summary of the invention
Target of the present invention is to provide a kind of method, and it can be with better conversion ratio and gratifying produced in yields unsaturated aldehyde and/or unsaturated carboxylic acid by at least a catalytic vapor phase oxidation that is selected from the compound of propylene, isobutene and the tert-butyl alcohol.
The present inventor has been found that by its deep investigation, above-mentioned target can be by following realization: will be filled in the reaction tube by multiple different types of catalyst that specific blend oxides different aspect the component kind of forming metal and/or content ratio is formed, increase from the feeding gas feeding gas outlet catalytic activity that enters the mouth thus, then feeding gas is fed in the reaction tube, and wherein this catalyst obtains by following: drying contains the aqueous solution or the water slurry of every kind of catalytic component, under the atmosphere of the gas that contains molecular oxygen, calcine then, subsequently heat treatment in the presence of reducing substances.Therefore, find to have realized the present invention based on the above.
Therefore the invention provides a kind of method that is used to produce unsaturated aldehyde and/or unsaturated carboxylic acid, may further comprise the steps:
In reaction tube charging contain the feeding gas of at least a compound that is selected from propylene, isobutene and the tert-butyl alcohol and molecular oxygen and
The described at least a compound of catalytic gas phase oxidation is to produce corresponding described unsaturated aldehyde and/or unsaturated carboxylic acid, wherein
(1) at least two kinds of catalyst with different catalytically active are filled in the reaction tube, increase from the feeding gas of the reaction tube feeding gas outlet catalytic activity that enters the mouth thus,
(2) catalyst comprises the mixed oxide by following formula (I) representative independently of one another:
Mo
aBi
bFe
cA
dB
eC
fD
gO
x (I)
Wherein
Mo, Bi and Fe represent molybdenum, bismuth and iron respectively,
A represents nickel and/or cobalt,
B represents at least a manganese, zinc, calcium, magnesium, tin and the plumbous element of being selected from,
C represents at least a element that is selected from phosphorus, boron, arsenic, tellurium, tungsten, antimony, silicon, aluminium, titanium, zirconium and cerium,
D represents at least a element that is selected from potassium, rubidium, caesium and thallium,
O represents oxygen,
A, b, c, d, e, f and g satisfy following relation: when a equals 12, and 0＜b≤10,0＜c≤10,1≤d≤10,0≤e≤10,0≤f≤10 and 0＜g≤2, and x be the value definite according to other element oxidation state,
(3) catalyst differ from one another aspect the kind of the metallic element that constitutes catalyst and/or the content ratio and
(4) catalyst obtains by following independently of one another: drying contains the aqueous solution or the water slurry of catalytic component, calcines under the atmosphere by the gas that contains molecular oxygen then, subsequently heat treatment in the presence of reducing substances.
According to the present invention, by at least a compound that is selected from propylene, isobutene and the tert-butyl alcohol of catalytic vapor phase oxidation, its corresponding unsaturated aldehyde and/or unsaturated carboxylic acid can be with gratifying yield with good conversion ratio productions.
Detailed Description Of The Invention
In the present invention, will contain the feeding gas of at least a compound that is selected from propylene, isobutene and the tert-butyl alcohol and molecular oxygen is fed to and is full of multiple catalyst with different catalytically active thus from the feeding gas reaction tube that feeding gas outlet catalytic activity increases that enters the mouth.The kind of catalyst is many more, and is more effective aspect the temperature control in reaction result and reaction tube, yet Preparation of catalysts or filling are also complicated more.Consider these factors, preferably use two kinds of catalyst.
The catalyst that the present invention uses is served as reasons independently of one another with the mixed oxide of following formula (I) representative:
Mo
aBi
bFe
cA
dB
eC
fD
gO
x (I)
Wherein
Mo, Bi and Fe represent molybdenum, bismuth and iron respectively,
A represents nickel and/or cobalt,
B represents at least a manganese, zinc, calcium, magnesium, tin and the plumbous element of being selected from,
C represents at least a element that is selected from phosphorus, boron, arsenic, tellurium, tungsten, antimony, silicon, aluminium, titanium, zirconium and cerium,
D represents at least a element that is selected from potassium, rubidium, caesium and thallium,
O represents oxygen,
When a equaled 12, a, b, c, d, e, f and g satisfied following relation: 0＜b≤10,0＜c≤10,1≤d≤10,0≤e≤10,0≤f≤10 and 0＜g≤2, and x is the value of determining according to other element oxidation state.
Catalyst is difference aspect the kind of the metallic element that constitutes catalyst and/or content ratio.At least a element that " catalyst is difference aspect the kind of the metallic element that constitutes catalyst " refers among a kind of A, B, C or the D of catalyst is different with the respective element of another kind of catalyst.In addition, " catalyst is in difference aspect the content ratio of the metallic element that constitutes catalyst " refers in one case, in a kind of catalyst when a is set to 12 the value of b, c, d, e, f and g respectively with in another catalyst when a is set to 12 the value of b, c, d, e, f and g relatively, at least one in a kind of catalyst in the value of b, c, d, e, f and g is different with the analog value in the another kind of catalyst.
Catalyst preferably includes by the mixed oxide with following formula (II) representative:
Mo
aBi
bFe
cCo
dSb
fCs
gO
x (II)：
Wherein Mo, Bi, Fe, Co, Sb and Cs represent molybdenum, bismuth, iron, cobalt, antimony and caesium respectively,
When a equaled 12, a, b, c, d, e, f and g satisfied following relation: 0＜b≤10,0＜c≤10,1≤d≤10,0≤e≤10,0≤f≤10 and 0＜g≤2, and x is the value of determining according to other element oxidation state.
In this case, catalyst is also inequality aspect the kind of the metallic element that constitutes catalyst and/or content ratio each other.
Catalyst with and in reaction tube in the preferred embodiment of occupied state, two kinds of catalyst are filled in the reaction tube, and will comprise that f wherein is not that a kind of catalyst of 0 formula (II) mixed oxide is filled in the reaction tube of feeding gas inlet side, to comprise that f wherein is that the another kind of catalyst of 0 formula (II) mixed oxide is filled in the reaction tube that feeding gas exports a side, and be filled into the molybdenum of the catalyst in the reaction tube of feed entrance one side, bismuth, the content ratio of iron and cobalt respectively be filled into the reaction tube that feeding gas exports a side in those content of catalyst identical.
Now, the method for the catalyst that preparation is used according to the invention is described below.The catalyst with different catalytically active that the present invention uses is prepared independently of one another.Raw material as this catalyst, the compound of forming the various elements of catalyst, for example oxide, nitrate, sulfate, carbonate, hydroxide, carbonate and ammonium salt thereof with and halide use the optimum content ratio that can satisfy element thus with certain proportion.For example molybdenum trioxide, molybdic acid, ammonium paramolybdate or the like can be used as molybdenum compound.Bismuth oxide, bismuth nitrate, bismuth sulfate or the like can be used as bismuth compound.Ferric nitrate (III), ferric sulfate (III), iron chloride (III) or the like can be used as iron compound.Cobalt nitrate, cobaltous sulfate, cobalt chloride or the like can be used as cobalt compound.Antimony trioxide, antimony chloride (III) or the like can be used as antimonial.Cesium nitrate, cesium carbonate, cesium hydroxide or the like can be used as cesium compound.
In the present invention, the aqueous solution or aqueous suspension can be by being blended in the catalyst raw material in the water, and drying solution or suspension prepare then.Then, drying composite is calcined in containing the atmosphere of molecular oxygen.Can after drying, add some catalyst raw material, for example antimonial.Each step can be carried out (for example referring to JP-A-59-46132, JP-A-60-163830 and JP-A-2000-288396) according to conventional methods.For example, drying can use kneading machine, chamber dryer, drum-type air dryer, spray dryer, flushing drier or the like to carry out.The concentration that contains molecular oxygen in the gas of molecular oxygen is generally 1 to 30 volume %, and preferred 10-25 volume %.Surrounding air or pure oxygen are usually as the molecular oxygen source.If necessary, this gas source is using nitrogen, carbon dioxide, water, helium, argon gas or the like dilution back as the gas that contains molecular oxygen usually.Calcining heat is generally 300-600 ℃, preferred 400-550 ℃.Calcination time is generally 5 minutes to 40 hours, preferred 1 to 20 hour.
To in the presence of reducing substances, heat-treat by the calcined product that calcining produces.This processing of carrying out in the presence of reducing substances abbreviates reduction hereinafter usually as and handles.
The example of reducing substances comprises for example hydrogen, ammonia, carbon monoxide, hydrocarbon, alcohol, aldehyde and amine.Randomly can use in these reducing materials two or more.Preferably each has 1 to about 6 carbon atoms for hydrocarbon, alcohol, aldehyde and amine.The example of this hydrocarbon comprises saturated aliphatic hydrocarbon, for example methane, ethane, propane, normal butane and iso-butane, and unsaturated aliphatic hydrocarbon is ethene, propylene, alpha-butylene, β-butylene and isobutene for example, and aromatic hydrocarbon benzene for example.The example of this alcohol comprises radical of saturated aliphatic alcohol for example methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, and unsaturated aliphatic alcohol is allyl alcohol, butenol and methallyl alcohol for example, and fragrant and mellow for example phenol.The example of this aldehyde comprises radical of saturated aliphatic aldehyde for example formaldehyde, acetaldehyde, propionic aldehyde, hutanal and isobutylaldehyde, and unsaturated aliphatic aldehyde for example methacrylaldehyde, crotonaldehyde and methacrolein.The example of this amine comprises representative examples of saturated aliphatic amine for example methylamine, dimethylamine, trimethylamine, ethamine, diethylamine and triethylamine, and unsaturated aliphatic amine is allylamine and diallylamine for example, and aromatic amine aniline for example.
Reduction is handled usually by making calcined product accept heat treatment under the atmosphere of the gas that contains reducing substances.The concentration of reducing substances is generally 0.1 to 50 volume % in the gas, and preferred 1 to 30 volume %.Reducing substances can be realized this concentration thus with nitrogen, carbon dioxide, water, helium, argon gas or the like dilution.Molecular oxygen is allowed existence, unless the effect that its influence reduction is handled.Yet, may not allow molecular oxygen to exist.
The temperature of handling that is used to reduce is generally 200-600 ℃, and preferred 250-550 ℃.The time that reduction is handled is generally 5 minutes to 20 hours, and preferred 30 minutes to 10 hours.Preferably calcined product is positioned in tubulose or the box describe device and keeps this container and the gas that contains reducing substances to ventilate to reduce processing.If necessary the gas that discharges from this container can be recycled and reuse this moment.
Reduction is handled and is caused mass loss usually.This may be because the grid oxygen atom loses from catalyst.The preferred mass loss is 0.05 to 6 quality %, and preferred 0.1 to 5 quality %.If surpass 6 quality % owing to excessive reduction makes mass loss, mass loss can be by calcining compensation once more in containing the atmosphere of molecular oxygen.
Mass loss can use following equation to calculate:
Mass loss (%)=100 * [(weight of calcined product is before handled in reduction)-(weight of calcined product after the reduction processing)]/(weight of calcined product before the reduction processing)
According to the kind of the reducing substances that uses, heat-treat condition or the like, in reduction was handled, reducing substances itself, catabolite of being obtained by reducing substances or the like can be retained in the catalyst after the reduction processing.In this case, mass loss can followingly be calculated: measure the weight of residue in the catalyst, calculate the weight after reduction is handled then, by deduct residue weight from the catalyst weight that contains residue.The residue of bent type is a charcoal, and therefore the weight of residue for example can pass through total carbon (TC) analysis and determines.
Catalyst is molded into required form usually, is used for the inventive method then.In molded, can catalyst be molded as ring, particle, ball or the like form by compressing tablet, extrusion mo(u)lding or the like.The shape of the catalyst that the present invention uses can be identical or different.Molded can carrying out before and after calcining in containing the atmosphere of molecular oxygen perhaps carries out after reduction is handled.When molded,, can described in JP-A-9-52053, add inorfil etc. and be the material of inertia basically specifying oxidation reaction in order to improve the mechanical strength of catalyst.
Therefore, prepared catalyst with different activities.The catalytic activity of each catalyst can be estimated by use at least a starting compound and the measurement conversion of compounds rate that is selected from propylene, isobutene and the tert-butyl alcohol of molecular oxygen catalytic gas phase oxidation in the presence of catalyst.Catalytic gas phase oxidation, so that catalytic activity that is, increases from the enter the mouth conversion ratio of feeding gas outlet of feeding gas, and provides the feeding gas and the molecular oxygen that contain starting compound to carry out by fill this catalyst in reaction tube.In industrial production, the preferred multitubular reactor of fixed bed that contains above-mentioned reaction tube that uses.
Air is used as the source of molecular oxygen usually.Except that starting compound and molecular oxygen, feeding gas can contain nitrogen, carbon dioxide, carbon monoxide, water vapour or the like.
By above-mentioned catalytic gas phase oxidation, methacrylaldehyde and/or acrylic acid can be produced by propylene with gratifying high yield.Perhaps, methacrolein and/or methacrylic acid can be produced by the isobutene or the tert-butyl alcohol with gratifying yield.
Reaction temperature is generally 250-400 ℃.Reaction pressure can be decompression, yet it typically is normal pressure to 500kPa.With respect to every mole of starting compound, the amount of molecular oxygen is generally 1 to 3 mole.The space velocity SV of feeding gas when STP (standard temperature and pressure (STP)) is generally 500-5000
-1
Embodiment
Embodiments of the invention are as follows, yet it does not limit the present invention by any way.In these embodiments except as otherwise noted, the flow velocity of unit " ml/min " expression gas when STP.In these embodiments, conversion ratio (%) and yield are defined as follows:
Conversion ratio (%)=[(charging isobutene mole)-(unreacted isobutene mole)]/(charging isobutene mole)
Total recovery (%)=100 * (integral molar quantity of methacrolein and methacrylic acid)/(charging isobutene mole)
Reference example 1
The preparation of catalyst a (the not catalyst of reduction processing)
With 4414 gram ammonium molybdate [(NH
4)
6Mo
7O
244H
2O] be dissolved in the 5000 gram warm water to form liquid A.With 2020 gram ferric nitrate (III) [Fe (NO
3)
39H
2O], 4366 gram cobalt nitrate [Co (NO
3)
26H
2O] and 195 gram cesium nitrate [CsNO
3] be dissolved in 2000 gram warm water and further dissolve 970 gram bismuth nitrate [Bi (NO subsequently
3)
35H
2O] to form liquid B.When stirring, liquid B is joined liquid A to form suspension.Use the flash distillation dryer dry suspension to obtain dried product then.(by the RFC400-SL of Saint-GobainTM production) joins in 100 parts of dry substance with 6 mass parts aluminium oxide-silicon oxide fibres.It is that 6.3 millimeters, internal diameter are that 2.5 millimeters and length are 6 millimeters annular that the gained mixture is molded as external diameter, flows down 525 ℃ of calcinings 6 hours to obtain catalyst a at air then.Per 12 molybdenum atoms, this catalyst contain 0.96 bismuth atom, 2.4 iron atoms, 7.2 cobalt atoms and 0.48 caesium atom.
Embodiment 1
The preparation of catalyst A (catalyst that reduction is handled)
By catalyst a is filled into glass tube, allows the mist of hydrogen/nitrogen (5/95 volume) flow through glass tube then and prepared catalyst A in 8 hours to reduce to handle at 350 ℃.Be similar to catalyst a, per 12 molybdenum atoms, this catalyst contain 0.96 bismuth atom, 2.4 iron atoms, 7.2 cobalt atoms and 0.48 caesium atom, and the mass loss that former processing produces is 0.90 quality %.
Reference example 2
The preparation of catalyst b (the not catalyst of reduction processing)
Except adding 2.54 mass parts antimony trioxide (Sb in the 100 mass parts drying materials in comparative example 1
2O
3) and calcining heat changed into outside 546 ℃, use with comparative example 1 in same method prepare catalyst b.Per 12 molybdenum atoms, this catalyst contain 0.96 bismuth atom, 0.48 antimony atoms, 2.4 iron atoms, 7.2 cobalt atoms and 0.48 caesium atom.
Embodiment 2
The preparation of catalyst B (catalyst that reduction is handled)
By catalyst b is filled in the glass tube, allows the mist of hydrogen/nitrogen (5/95 volume) flow through glass tube then and prepared catalyst B in 8 hours to reduce to handle at 350 ℃.Be similar to catalyst b, per 12 molybdenum atoms, this catalyst contain 0.96 bismuth atom, 0.48 antimony atoms, 2.4 iron atoms, 7.2 cobalt atoms and 0.48 caesium atom, and the mass loss that former processing produces is 1.28 quality %.
Reference example 3
The preparation of catalyst c (the not catalyst of reduction processing)
Except the amount with cesium nitrate changed 273 grams into, method same among use and the comparative example 1 prepared catalyst c.Per 12 molybdenum atoms, this catalyst contain 0.96 bismuth atom, 2.4 iron atoms, 7.2 cobalt atoms and 0.67 caesium atom.
Embodiment 3
Catalyst C preparation (catalyst that reduction is handled)
By catalyst c is filled in the glass tube, allows the mist of hydrogen/nitrogen (5/95 volume) flow through glass tube then and prepared catalyst C in 8 hours to reduce to handle at 350 ℃.Be similar to catalyst c, per 12 molybdenum atoms, this catalyst contain 0.96 bismuth atom, 2.4 iron atoms, 7.2 cobalt atoms and 0.67 caesium atom, and the mass loss that former processing produces is 0.77 quality %.
Reference example 4
The preparation of catalyst d (the not catalyst of reduction processing)
With 6 mass parts aluminium oxide-silicon oxide fibres (by the RFC400-SL of Saint-Gobain TM production) and 2.54 mass parts antimony trioxide (Sb
2O
3) join in 100 parts of dry substance that obtain among the comparative example 3.It is that 6.3 millimeters, internal diameter are that 2.5 millimeters and length are 6 millimeters annular that the gained mixture is molded as external diameter, flows down 490 ℃ of calcinings 6 hours to obtain catalyst d at air then.Per 12 molybdenum atoms, this catalyst contain 0.96 bismuth atom, 0.29 antimony atoms, 2.4 iron atoms, 7.2 cobalt atoms and 0.67 caesium atom.
Embodiment 4
Catalyst D preparation (catalyst that reduction is handled)
By catalyst D is filled in the glass tube, allows the mist of hydrogen/nitrogen (5/95 volume) flow through glass tube then and prepared catalyst D in 8 hours to reduce to handle at 350 ℃.Be similar to catalyst b, per 12 molybdenum atoms, this catalyst contain 0.96 bismuth atom, 0.29 antimony atoms, 2.4 iron atoms, 7.2 cobalt atoms and 0.67 caesium atom, and the mass loss that former processing produces is 1.17 quality %.
Comparing embodiment 1
Use the oxidation of catalyst A (catalyst A individual layer)
14.30 milliliters of catalyst A are used to be filled in internal diameter after the 30 gram diamond dust dilutions be (the SHINANO-RUNDUM GC F16 that is produced by Shinano Electric Refining Co., Ltd) in 18 millimeters the glass reactor.By the mist of isobutene/oxygen/nitrogen/water vapour (1.0/2.2/6.2/2.0 mole) is fed to reaction tube with the flow velocity of 157.5 ml/min, under 330 ℃ reaction temperature, carry out oxidation reaction.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Comparing embodiment 2
Use the oxidation of catalyst A (catalyst A individual layer)
Except reaction temperature being become 340 ℃, with carrying out oxidation reaction with comparing embodiment 1 the same method.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Comparing embodiment 3
Use the oxidation of catalyst A (catalyst A individual layer)
Except reaction temperature being become 350 ℃, with carrying out oxidation reaction with comparing embodiment 1 the same method.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Comparing embodiment 4
Use catalyst B oxidation (catalyst B individual layer)
Except catalyst A is changed into the catalyst B, with carrying out oxidation reaction with comparing embodiment 1 the same method.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Comparing embodiment 5
Use the oxidation of catalyst C (catalyst C individual layer)
Except catalyst A being changed into catalyst C and reaction temperature being become 340 ℃, with carrying out oxidation reaction with comparing embodiment 1 the same method.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Comparing embodiment 6
Use the oxidation of catalyst D (catalyst D individual layer)
Except catalyst A being changed into catalyst D and reaction temperature being become 350 ℃, with carrying out oxidation reaction with comparing embodiment 1 the same method.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Embodiment 5
Use the oxidation of catalyst B and A (catalyst B/catalyst A bilayer)
With 7.15 milliliters of catalyst B use be filled in after the 15 gram diamond dust dilution dilutions internal diameter be in 18 millimeters the glass reactor near feeding gas inlet side (the SHINANO-RUNDUM GC F16 that produces by Shinano Electric Refining Co., Ltd), and 7.15 milliliters of catalyst B used to be filled near feeding gas after the 15 gram diamond dust dilution dilutions export a side (the SHINANO-RUNDUM GC F16 that ShinanoElectric Refining Co., Ltd produces).By the mist of isobutene/oxygen/nitrogen/water vapour (1.0/2.2/6.2/2.0 mole) is fed to reaction tube with the flow velocity of 157.5 ml/min, under 330 ℃ reaction temperature, carry out oxidation reaction.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Embodiment 6
Use the oxidation of catalyst C and A (catalyst C/ catalyst A bilayer)
Except catalyst B being changed into catalyst C and reaction temperature being become 340 ℃, with carrying out oxidation reaction with embodiment 5 the same methods.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Embodiment 7
Use the oxidation of catalyst D and A (catalyst D/ catalyst A bilayer)
Except catalyst B being changed into catalyst D and reaction temperature being become 350 ℃, with carrying out oxidation reaction with embodiment 5 the same methods.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Comparing embodiment 7
Use the oxidation of catalyst b and a (catalyst b/ catalyst a bilayer)
Except catalyst B and catalyst A are changed into respectively catalyst b and the catalyst a, with carrying out oxidation reaction with embodiment 5 the same methods.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Comparing embodiment 8
Use the oxidation of catalyst c and a (catalyst c/ catalyst a bilayer)
Except catalyst B and catalyst A being changed into catalyst c and catalyst a respectively and reaction temperature being changed into 340 ℃, with carrying out oxidation reaction with embodiment 5 the same methods.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Comparing embodiment 9
Use the oxidation of catalyst d and a (catalyst d/ catalyst a bilayer)
Except catalyst B and catalyst A being changed into catalyst d and catalyst a respectively and reaction temperature being changed into 350 ℃, with carrying out oxidation reaction with embodiment 5 the same methods.The total recovery of conversion for isobutene and methacrolein and methacrylic acid is as shown in table 1.
Table 1
Claims (8)
1. method that is used to produce unsaturated aldehyde and/or unsaturated carboxylic acid may further comprise the steps:
In reaction tube charging contain the feeding gas of at least a compound that is selected from propylene, isobutene and the tert-butyl alcohol and molecular oxygen and
The described at least a compound of catalytic oxidation in gas phase is to produce corresponding described unsaturated aldehyde and/or unsaturated carboxylic acid, wherein
(1) at least two kinds of catalyst with different catalytically active are filled in the reaction tube, increase from the feeding gas of the reaction tube feeding gas outlet catalytic activity that enters the mouth thus,
(2) catalyst comprises the mixed oxide by following formula (I) representative independently of one another:
Mo
aBi
bFe
cA
dB
eC
fD
gO
x (I)
Wherein
Mo, Bi and Fe represent molybdenum, bismuth and iron respectively,
A represents nickel and/or cobalt,
B represents at least a manganese, zinc, calcium, magnesium, tin and the plumbous element of being selected from,
C represents at least a element that is selected from phosphorus, boron, arsenic, tellurium, tungsten, antimony, silicon, aluminium, titanium, zirconium and cerium,
D represents at least a element that is selected from potassium, rubidium, caesium and thallium,
O represents oxygen,
A, b, c, d, e, f and g satisfy following relation: when a equals 12, and 0＜b≤10,0＜c≤10,1≤d≤10,0≤e≤10,0≤f≤10 and 0＜g≤2, and x be the value definite according to other element oxidation state,
(3) catalyst differ from one another aspect the kind of the metallic element that constitutes catalyst and/or the content and
(4) catalyst obtains by following independently of one another: drying contains the aqueous solution or the water slurry of catalytic component, calcines under the atmosphere of the gas that contains molecular oxygen then, subsequently heat treatment in the presence of reducing substances.
2. according to the process of claim 1 wherein that catalyst comprises independently of one another by the mixed oxide with following formula (II) representative:
Mo
aBi
bFe
cCo
dSb
fCs
gO
x (II)：
Wherein Mo, Bi, Fe, Co, Sb and Cs represent molybdenum, bismuth, iron, cobalt, antimony and caesium respectively,
When a equaled 12, a, b, c, d, e, f and g satisfied following relation: 0＜b≤10,0＜c≤10,1≤d≤10,0≤e≤10,0≤f≤10 and 0＜g≤2, and x is the value of determining according to other element oxidation state.
3. according to the method for claim 1 or 2, the species number that wherein is filled into the catalyst in the reaction tube is 2.
4. according to the method for claim 3, to comprise that wherein f wherein is not that a kind of catalyst of the mixed oxide of 0 formula (II) is filled in the reaction tube of feeding gas inlet side, and comprising that f wherein is that the another kind of catalyst of the mixed oxide of 0 formula (II) is filled in the reaction tube that feeding gas exports a side, and be filled into the catalyst in the reaction tube of feeding gas inlet side molybdenum, bismuth, iron and cobalt content ratio respectively be filled into the reaction tube that feeding gas exports a side in those content of catalyst identical.
5. according to any described method among the claim 1-4, wherein calcine at 300-600 ℃ and carry out.
6. according to any described method among the claim 1-5, wherein heat treatment is carried out at 200-600 ℃.
7. according to any described method among the claim 1-6, wherein the catalyst quality loss that produces owing to heat treatment is 0.05-6 quality %.
8. according to any described method among the claim 1-7, wherein reducing substances is at least a following compound that is 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 amine of 1-6 carbon atom.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007074381A JP5045175B2 (en) | 2007-03-22 | 2007-03-22 | Process for producing unsaturated aldehyde and / or unsaturated carboxylic acid |
| JP2007-074381 | 2007-03-22 |
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| Publication Number | Publication Date |
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| CN101269333A true CN101269333A (en) | 2008-09-24 |
| CN101269333B CN101269333B (en) | 2012-10-03 |
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| Country | Link |
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| JP (1) | JP5045175B2 (en) |
| KR (1) | KR101513300B1 (en) |
| CN (1) | CN101269333B (en) |
| SG (1) | SG146559A1 (en) |
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| CN1062550C (en) * | 1993-06-25 | 2001-02-28 | 住友化学工业株式会社 | Process for production of unsaturated aldehyde and unsaturated carboxylic acid |
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| JP4265621B2 (en) * | 2006-06-06 | 2009-05-20 | 住友化学株式会社 | Process for producing unsaturated aldehyde and unsaturated carboxylic acid |
-
2007
- 2007-03-22 JP JP2007074381A patent/JP5045175B2/en not_active Expired - Fee Related
-
2008
- 2008-03-11 SG SG200802045-5A patent/SG146559A1/en unknown
- 2008-03-20 KR KR1020080025685A patent/KR101513300B1/en not_active IP Right Cessation
- 2008-03-21 CN CN2008100830666A patent/CN101269333B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20080086365A (en) | 2008-09-25 |
| SG146559A1 (en) | 2008-10-30 |
| JP2008231044A (en) | 2008-10-02 |
| CN101269333B (en) | 2012-10-03 |
| KR101513300B1 (en) | 2015-04-17 |
| JP5045175B2 (en) | 2012-10-10 |
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