CN106582677B - A kind of preparation method and its usage of more metal composite oxide catalysts - Google Patents
A kind of preparation method and its usage of more metal composite oxide catalysts Download PDFInfo
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- CN106582677B CN106582677B CN201611088074.0A CN201611088074A CN106582677B CN 106582677 B CN106582677 B CN 106582677B CN 201611088074 A CN201611088074 A CN 201611088074A CN 106582677 B CN106582677 B CN 106582677B
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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
- 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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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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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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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a kind of preparation method and its usages of more metal composite oxide catalysts.The preparation method of the catalyst is that the solution A containing molybdenum element and the solution B containing bismuth element obtain slurries a by the way of co-precipitation, and slurries a passes through drying, and roasting obtains final catalyst after molding.The water content before solution A, the water of B and slurries a are dried is controlled, and slurry a is dried in the lower atmosphere of oxygen content.For the catalyst prepared using the method in alkene Selective Oxidation unsaturated aldehyde and/or carboxylic acid, hot(test)-spot temperature is low, and catalyst strength is high, has heat release few, and selectivity is high, the advantage of service life length.
Description
Technical field
The invention belongs to catalyst fields, and in particular to one kind prepares more metals of unsaturated aldehyde (acid) for olefin oxidation
Composite oxide catalysts and preparation method thereof.
Background technique
The reaction that unsaturated aldehyde and/or carboxylic acid are prepared by the chosen oxidation of alkene, as Selective Oxidation of Propylene acrolein and/
Or acrylic acid, the industrializeding catalyst of isobutene (or tert-butyl alcohol) Selective Oxidation methacrolein and/or methacrylic acid is
Know mainly by molybdenum, bismuth be indispensable element metal composite oxide form, this kind of catalyst usually also containing iron, cobalt, nickel, copper and
At least one of elements such as zinc.
For the preparation method of alkene Selective Oxidation unsaturated aldehyde and/or the O composite metallic oxide catalyst of carboxylic acid,
Many improvement projects have been proposed, as CN100423837C obtains high activity, high yield by using the mode of microwave drying
The catalyst of rate, CN1314487C usually improve the work of catalyst by the way that the member such as Sb, Pb, Yb is added in catalyst preparation process
Property and stability, CN101066528B mention the pore size distribution by controlling catalyst to improve conversion ratio and the selection of catalyst
Property.Since isobutene or Oxidation of t-Butanol preparation methacrolein are a strong exothermal reactions, the above catalyst is applied to isobutyl
In alkene or Oxidation of t-Butanol preparation methacrolein, there is a problem of that hot(test)-spot temperature is excessively high, this problem, which will lead to, to play a major role
Oxidation activity component Mo be lost during the reaction, and then shorten catalyst service life.
It is hot when CN101385978B makes catalyst reaction in such a way that active component is mixed with carriers such as graphite, boron, silicon
Point temperature decreases, but hot spot is still higher, and graphite is added in active component, after the carriers such as silicon form together, causes to form
Catalyst strength decline, easy dusting, easily causes reactor pressure decrease to increase in use, also will cause " temperature runaway " phenomenon, urges
Agent service life is greatly affected.
It, should the problem of preformed catalyst intensity difference in conclusion the generally existing hot(test)-spot temperature of existing catalyst is high at present
Problem will cause catalyst active principle volatilization and the problems such as catalyst dusting in use, will be greatly reduced catalyst
Service life.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of more metal composite oxide catalysts, solve in the prior art
Catalyst bed hot-spot causes catalyst life bad, the not high problem of activity.Make preparation gained catalyst reach reduction to urge
Agent hot(test)-spot temperature improves catalyst service life and improves the purpose of catalyst activity.
The present invention prepares the catalyst that hot(test)-spot temperature is low, selectivity is high by each process conditions in control preparation process,
And the ball shape catalyst that high glossy and high intensity are prepared by the partial size of catalyst precarsor when control molding, can be big
The big service life for extending catalyst.
To achieve the above objectives, the invention adopts the following technical scheme:
A kind of preparation method of more metal composite oxide catalysts, comprising the following steps:
(1) solution A containing molybdenum element and the solution B containing bismuth element are prepared；
(2) solution A and B are subjected to mixed precipitation, obtain slurry a；
(3) solid content of slurry a is adjusted by adjusting water content；
(4) the slurry a that drying steps (3) obtain, obtains catalyst precarsor；
(5) catalyst precarsor that step (4) obtains is formed, roasts, obtains catalyst.
Solution A can also contain one of sodium, potassium, rubidium and caesium in addition to containing molybdenum element in step (1) of the present invention
Or multiple element.The mass ratio of water and molybdenum element in the solution A is 3~40:1, preferably 6~20:1.
Except containing in addition to bismuth element in solution B in step (1) of the present invention, can also containing iron, cobalt, nickel, copper, zinc, lead,
One of manganese, niobium and tungsten or multiple element.The mass ratio of water and bismuth element in the solution B be 1~22:1, preferably 3
~15:1.
The corresponding source of contained element is without specifically limited, preferably water-soluble or acid in solution A or solution B of the present invention
The compound of dissolubility.For example, as molybdenum source such as containing the compound of molybdenum, the molybdenum oxides such as optional molybdenum trioxide, molybdic acid, seven molybdic acids
One of the molybdic acids or its salt such as ammonium, ammonium tetramolybdate, ammonium dimolybdate are a variety of, preferably water-soluble preferable ammonium heptamolybdate；Make
For the compound of bismuth-containing, in the bismuths oxide such as the bismuth salts such as optional bismuth nitrate, waltherite, bismuth chloride, bismuth acetate and bismuth trioxide
It is one or more, preferably acid soluble bismuth nitrate；As the starting material for containing other component elements, optional corresponding metal member
One of nitrate, carbonate, chloride, hydroxide, acylate, oxide or ammonium salt of element etc. are a variety of, preferably
Use one of its nitrate and ammonium salt or a variety of.The compound of respective element can be used alone, can also be two or more
Be used in mixed way, if using when ensure that solution A or solution B are clear transparent solutions.
The mass ratio of the water in water and solution B in solution A of the present invention be 0.2~8:1, preferably 0.5~4:
1。
The mixing of solution A and solution B is essentially precipitation process in step (2) of the present invention, and can take will be molten
Liquid A is added to the mode in solution B, or can also take the mode being added to solution B in solution A, preferably takes solution B
Be added in solution A and mixed within a certain period of time, and in mixed process with stirring and heating, incorporation time be 0.2~
5h, preferably 0.5~2h, mixing temperature are 40~100 DEG C, preferably 60~95 DEG C.
Gained mixed slurry a can directly be carried out step (3) after solution A and solution B mixing of the present invention；Preferably through ripe
Step (3) are carried out again after change processing；It is cured again after the pH of mixed slurry a is more preferably adjusted to 1~4 with ammonium hydroxide, when curing
Between for 0.5~for 24 hours, preferably 1~20h, curing temperature is 30~100 DEG C, preferably 50~90 DEG C.
Its water is preferably made by the water of the methods of evaporation or addition water control slurry a in step (3) of the present invention
Mass ratio with bismuth element is 2~14:1, preferably 5~12:1.The mode of evaporation water can be agitating and heating in oil bath
Can carry out heating in an oven makes slurry a volatile fraction moisture, and preferably heating makes its a part of water that volatilizees in oil bath.Pass through reality
It tests and shows that the water of slurry a can change the hot spot in the use process of catalyst, the water by optimizing slurry a can obtain
It is lower to hot(test)-spot temperature, the higher catalyst of target product selectivity.
Step (4) of the present invention need to control under the atmosphere that oxygen content is 6~15v% when slurry a is dried
It carries out, preferably oxygen content is 7~12v%.Drying mode is not particularly limited, and can be used known in the art any dry
The group of drying method, such as evaporation drying, vacuum drying, drum dried, spray drying, expansion drying etc. or above-mentioned drying means
It closes, in order to facilitate the molding procedure of step (5), it is preferred to use the spray drying process that powdered hirudo leech can be obtained more preferably is adopted
With centrifugal spray drying method.Under the atmosphere of oxygen content of the present invention, it is more advantageous between each metallic element of catalyst and is formed
Composite oxides, rather than metallic element is respectively individually formed oxide, is conducive to improve the effective of (methyl) methacrylaldehyde in this way
Selectivity.
As forming method described in step (5), compression molding, extrusion molding or granulating and forming etc. can be used, according to
It needs catalyst that can be molded as required shapes, the present invention such as cylindric, cyclic annular or spherical preferably to coat catalyst precarsor
Become spheric catalyst on sphere inert carrier.The diameter of the sphere inert carrier be 3~5mm, preferably 3.5~
4.5mm；Water absorption rate is 5~50wt%, preferably 10~20wt%.The mass ratio of sphere inert carrier and outer layer catalyst precursor is
0.5~3.0:1, preferably 1.0~2.0:1.When being coated in catalyst precarsor on sphere inert carrier when molding, preferably takes and add
Enter silica solution as binder.
The catalyst precarsor that different-grain diameter range can be used when molding is formed, preferable particle size 30-50um and 0.1-
The catalyst precarsor of two ranges of 10um is used in mixed way.And the two mass ratio is controlled in 0.2~30:1, preferably 0.5
~20:1.The smoothness and intensity that molding rear catalyst can be increased, are not pulverized easily catalyst, prevent dusting from causing pressure drop
Raising and " temperature runaway " phenomenon, extend the service life of catalyst.
The method of roasting of preformed catalyst is not particularly limited, and any conventional roasting side known in the art can be used
Method, maturing temperature are 400~600 DEG C, and preferably 450~550 DEG C, calcining time is 2~10h.
More metal composite oxide catalysts of the method for the invention preparation, active component following general formula:
Mo12BiaAbBcOx, wherein A is selected from one of sodium, potassium, rubidium and caesium or a variety of, and B is selected from iron, cobalt, nickel, copper, zinc, lead, manganese, niobium
With one of tungsten or a variety of.A, b, c respectively represent the atomic ratio of respective components, and a=0.5~6, preferably a=1~5 are more excellent
Select a=1.5~4.5；B=0~8, preferably b=0.01~5, more preferable b=0.02~3；C=0~20, preferably c=0.1~
15, more preferable c=0.5~10；X is the atomic ratio of oxygen required for meeting each element chemical valence.
More metal composite oxide catalysts of the present invention can be applied to alkene Selective Oxidation unsaturated aldehyde and/or
Carboxylic acid, such as Selective Oxidation of Propylene acrolein and/or acrylic acid, isobutene (or tert-butyl alcohol) Selective Oxidation methacrolein
And/or methacrylic acid.
Raw material olefin, the dilute gas mixture of air or molecule-containing keto and vapor it is preheated after, be passed through equipped with catalysis
Reaction synthesis unsaturated aldehyde and/or carboxylic acid are carried out in the fixed-bed tube reactor of agent.The diluent gas of molecule-containing keto used is mixed
It closes in object, molecular oxygen may come from pure oxygen, oxygen-enriched or air, and diluent gas can be N2、CO2With one of vapor or
It is a variety of.
When being loaded in fixed-bed tube reactor using catalyst of the present invention, it is preferred to use undiluted side
Formula is loaded, and such olefin conversion can be optimal, and not occur the phenomenon that temperature runaway still in driving process, and by
In using filling scheme is not diluted, the hotspot location of catalyst has delayed to move down due to hotspot location closer to gas access side
Caused by catalyst activity reduction so that the service life of catalyst further extends.
When reaction of the catalyst of the invention for catalyzed alkene Selective Oxidation unsaturated aldehyde and/or carboxylic acid, condition are as follows:
250~360 DEG C of reaction temperature, preferably 280~340 DEG C；Reaction pressure is 0.01~0.15MPa of absolute pressure, preferably normal pressure；Instead
The air speed for answering material mixed gas is 400~4000h-1, preferably 800~2000h-1；Alkene molar concentration in gaseous mixture is 1~
15%, preferably 3~10%；O2Molar ratio with alkene is 0.1~7:1, preferably 0.5~4:1；The molar ratio of vapor and alkene
0.1~10:1, preferably 0.5~5:1.
More metal composite oxide catalysts of the present invention for catalyzed alkene Selective Oxidation unsaturated aldehyde and/or
When the reaction of carboxylic acid, reaction hot spot can be reduced, reduces the loss of active principle molybdenum element in catalyst use process, and is mentioned
The high effective selectivity of target product.The present invention improves catalysis by mixing the catalyst precarsor of two particle size ranges simultaneously
Agent moulding process, prepare high glossy and high intensity ball shape catalyst, can by the abrasion index of ball shape catalyst by
1% or so is promoted to 0.5% or so, and abrasion index reaches 0.3% when intensity highest after optimization mixed proportion.Ball shape catalyst is strong
The raising of degree, substantially increases the service life of catalyst at the problem of avoiding dusting in catalyst use process.
Specific embodiment
Catalyst provided by present invention be described in more detail by the following examples and preparation method thereof, but the present invention
Therefore it is not any way limited.
The calculating of the selectivity of propylene, isobutene or tert-butyl alcohol conversion ratio and any product (being indicated in formula with X product)
Method is described as follows:
The conversion ratio of propylene, isobutene or the tert-butyl alcohol={ (C atomic molar number contained by reaction product)/(reaction raw materials
Contained C atomic molar number) } × 100%；
The selectivity of X product={ (C atomic molar number contained by X product)/(C atomic molar number contained by reaction product) } ×
100%.
The rate of wear of catalyst tests reference standard: HG/T 2976-1999 (measurement of chemical fertilizer catalyst rate of wear), test
Instrument is KM-5A particle abrasion test instrument (production of Dalian Peng Hui Science and Technology Development Co., Ltd.)
Embodiment 1
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 1000g deionization
In water, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O,
110g ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2It is molten that O puts into the nitric acid that 200g mass concentration is 3%
In liquid, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added in 30min molten
In liquid A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is obtained
Slurry a continues to heat slurry a under open state, until slurry a evaporates 900ml water.Then slurry a is spray-dried, is sprayed
Control inlet temperature is 250 DEG C when mist is dry, 120 DEG C of outlet temperature, and use atmosphere for nitrogen in spray-drying process and
The low oxygen content method gaseous mixture of volume of air ratio 1:1.Later, it will be spray-dried resulting partial size 30-50um's and 0.1-10um
The powder of two ranges is coated on porous inert porcelain ball (outer diameter 4.0mm, water absorption rate 15%) according to mass ratio in 28:1 mixing,
Carrier and the mass ratio of outer layer active component are 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9N 0.4Cs0.16Ox.Abrasion index is 0.7%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 383 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.5%, and methacrolein is selectively 86.5%, Methacrylic acid selectivity 2%, continuous anti-under this condition
After answering 4000h, hot(test)-spot temperature is 385 DEG C, and isobutene conversion 99.7%, methacrolein is selectively 85.5%, methyl
Acrylic acid selectivity 2.5%.
Embodiment 2
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 9000g deionization
In water, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O,
110g ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2O puts into the nitric acid that 2400g mass concentration is 3%
In solution, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added in 30min
In solution A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is obtained
To slurry a, continue to heat slurry a under open state, until slurry a evaporates 9800ml water.Then slurry a is done by spraying
Dry, control inlet temperature is 250 DEG C when spray drying, 120 DEG C of outlet temperature, and use atmosphere for nitrogen in spray-drying process
The low oxygen content method gaseous mixture of gas and volume of air ratio 1:1.Later, resulting partial size 30-50um and 0.1- will be spray-dried
The powder of two ranges of 10um is coated on porous inert porcelain ball (outer diameter 4.0mm, water suction in 0.3:1 mixing according to mass ratio
Rate 15%), the mass ratio of carrier and outer layer active component is 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9Ni0.4Cs0.16Ox.It is 0.5% that abrasion index, which is surveyed,.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 384 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.6%, and methacrolein is selectively 85.9%, Methacrylic acid selectivity 2.3%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 387 DEG C, and isobutene conversion 99.7%, methacrolein is selectively 85.2%, first
Base acrylic acid selectivity 2.5%.
Embodiment 3
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 4500g deionization
In water, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O,
110g ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2O puts into the nitric acid that 1200g mass concentration is 3%
In solution, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added in 30min
In solution A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is obtained
To slurry a, continue to heat slurry a under open state, until slurry a evaporates 4400ml water.Then slurry a is done by spraying
Dry, control inlet temperature is 250 DEG C when spray drying, 120 DEG C of outlet temperature, and use atmosphere for nitrogen in spray-drying process
The low oxygen content method gaseous mixture of gas and volume of air ratio 1:1.Later, resulting partial size 30-50um and 0.1- will be spray-dried
The powder of two ranges of 10um is coated in (outer diameter 4.0mm, water absorption rate on porous inert porcelain ball in 15:1 mixing according to mass ratio
15%), carrier and the mass ratio of outer layer active component are 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9Ni0.4Cs0.16Ox.Abrasion index is 0.4%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 380 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.4%, and methacrolein is selectively 86.7%, Methacrylic acid selectivity 2%, continuous anti-under this condition
After answering 4000h, hot(test)-spot temperature is 382 DEG C, and isobutene conversion 99.6%, methacrolein is selectively 86.1%, methyl
Acrylic acid selectivity 2.3%.
Comparative example 1
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 500g deionized water
In, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O, 110g
Ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2O puts into the nitric acid solution that 700g mass concentration is 3%
In, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added to solution A in 30min
In, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is starched
Expect a, continue to heat slurry a under open state, until slurry a evaporates 400ml water.Then slurry a is spray-dried, it is spraying
Control inlet temperature is 250 DEG C when dry, 120 DEG C of outlet temperature, and use atmosphere in spray-drying process is nitrogen and sky
The low oxygen content method gaseous mixture of air volume ratio 1:1.Later, the two of resulting partial size 30-50um and 0.1-10um will be spray-dried
The powder of a range is coated on porous inert porcelain ball (outer diameter 4.0mm, water absorption rate 15%) according to mass ratio in 20:1 mixing, is carried
Body and the mass ratio of outer layer active component are 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9Ni0.4Cs0.16Ox.Abrasion index is 0.5%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 395 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.1%, and methacrolein is selectively 85.5%, Methacrylic acid selectivity 2.1%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 397 DEG C, and isobutene conversion 99.3%, methacrolein is selectively 83.2%, first
Base acrylic acid selectivity 2.2%.
Comparative example 2
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 3000g deionization
In water, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O,
110g ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2O puts into the nitric acid that 3000g mass concentration is 3%
In solution, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added in 30min
In solution A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is obtained
To slurry a, continue to heat slurry a under open state, until slurry a evaporates 5000ml water.Then slurry a is done by spraying
Dry, control inlet temperature is 250 DEG C when spray drying, 120 DEG C of outlet temperature, and use atmosphere for nitrogen in spray-drying process
The low oxygen content method gaseous mixture of gas and volume of air ratio 1:1.Later, resulting partial size 30-50um and 0.1- will be spray-dried
The powder of two ranges of 10um is coated in (outer diameter 4.0mm, water absorption rate on porous inert porcelain ball in 20:1 mixing according to mass ratio
15%), carrier and the mass ratio of outer layer active component are 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9Ni0.4Cs0.16Ox.Abrasion index is 0.4%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 397 DEG C after successive reaction 100h, isobutene
Conversion ratio is 98.8%, and methacrolein is selectively 85.8%, Methacrylic acid selectivity 2.5%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 403 DEG C, and isobutene conversion 98.8%, methacrolein is selectively 82.5%, first
Base acrylic acid selectivity 1.8%.
Comparative example 3
(1) preparation of catalyst
By 440g ammonium heptamolybdate, 3.5g potassium nitrate is put into 70 DEG C of 4000g deionized water, is obtained after being completely dissolved molten
Liquid A.By 280g bismuth nitrate, 380g cobalt nitrate, 110g ferric nitrate, 110g nickel nitrate puts into the nitre that 1200g mass concentration is 3%
In acid solution, stirring is until obtain clear transparent solutions B；In the case where 70 DEG C of lasting stirrings, solution B is added in 60min
Into solution A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours,
It is down to room temperature, obtains slurry a；Continue to heat slurry a under open state, until slurry a evaporates 1000ml water.Then to slurry a
It is spray-dried, control inlet temperature is to be spray-dried at 250 DEG C, 120 DEG C of outlet temperature when spray drying.And it does by spraying
Use atmosphere for the low oxygen content method gaseous mixture of nitrogen and volume of air ratio 1:1 during dry.Later, it will be spray-dried resulting
Partial size 30-50um is mixed in 20:1 according to mass ratio with the powder of two ranges of 0.1-10um and is coated on porous inert porcelain ball
The mass ratio of (outer diameter 4.0mm, water absorption rate 15%), carrier and outer layer active component is 1.3:1.
Molding obtained above is placed in Muffle furnace in 480 DEG C of roasting 5h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co6.2Ni1.8K0.16Ox.Abrasion index is 0.4%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, and air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 395 DEG C after successive reaction 100h, isobutene
Conversion ratio is 98.5%, and methacrolein is selectively 85.7%, Methacrylic acid selectivity 2.3%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 403 DEG C, and isobutene conversion 98.7%, methacrolein is selectively 82.5%, first
Base acrylic acid selectivity 1.5%.
Comparative example 4
(1) preparation of catalyst
By 440g ammonium heptamolybdate, 3.5g potassium nitrate is put into 70 DEG C of 4500g deionized water, is obtained after being completely dissolved molten
Liquid A.By 280g bismuth nitrate, 380g cobalt nitrate, 110g ferric nitrate, 110g nickel nitrate puts into the nitre that 1200g mass concentration is 3%
In acid solution, stirring is until obtain clear transparent solutions B；In the case where 70 DEG C of lasting stirrings, solution B is added in 60min
Into solution A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours,
It is down to room temperature, obtains slurry a；Continue to heat slurry a under open state, until slurry a evaporates 4400ml water.Then to slurry a
It is spray-dried, control inlet temperature is to be spray-dried at 250 DEG C, 120 DEG C of outlet temperature when spray drying.And it does by spraying
Use atmosphere for the low oxygen content method gaseous mixture of nitrogen and volume of air ratio 1:1 during dry.Later, it will be spray-dried resulting
Partial size 30-50um is mixed in 0.1:1 according to mass ratio with the powder of two ranges of 0.1-10um and is coated in porous inert porcelain ball
The mass ratio of upper (outer diameter 4.0mm, water absorption rate 15%), carrier and outer layer active component is 1.3:1.
Molding obtained above is placed in Muffle furnace in 480 DEG C of roasting 5h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co6.2Ni1.8K0.16Ox.Abrasion index is 1.2%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 380 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.3%, and methacrolein is selectively 86.7%, Methacrylic acid selectivity 2.3%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 406 DEG C, and isobutene conversion 99.7%, methacrolein is selectively 82.5%, first
Base acrylic acid selectivity 2.8%.
Comparative example 5
(1) preparation of catalyst
By 440g ammonium heptamolybdate, 3.5g potassium nitrate is put into 70 DEG C of 4500g deionized water, is obtained after being completely dissolved molten
Liquid A.By 280g bismuth nitrate, 380g cobalt nitrate, 110g ferric nitrate, 110g nickel nitrate puts into the nitre that 1200g mass concentration is 3%
In acid solution, stirring is until obtain clear transparent solutions B；In the case where 70 DEG C of lasting stirrings, solution B is added in 60min
Into solution A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours,
It is down to room temperature, obtains slurry a；Continue to heat slurry a under open state, until slurry a evaporates 4400ml water.Then to slurry a
It is spray-dried, control inlet temperature is to be spray-dried at 250 DEG C, 120 DEG C of outlet temperature when spray drying.And it does by spraying
Use atmosphere for the low oxygen content method gaseous mixture of nitrogen and volume of air ratio 1:1 during dry.Later, it will be spray-dried resulting
Partial size 30-50um is mixed in 45:1 according to mass ratio with the powder of two ranges of 0.1-10um and is coated on porous inert porcelain ball
The mass ratio of (outer diameter 4.0mm, water absorption rate 15%), carrier and outer layer active component is 1.3:1.
Molding obtained above is placed in Muffle furnace in 480 DEG C of roasting 5h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co6.2Ni1.8K0.16Ox.Abrasion index is 1.0%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 382 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.5%, and methacrolein is selectively 86.5%, Methacrylic acid selectivity 2.1%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 408 DEG C, and isobutene conversion 99.7%, methacrolein is selectively 81.5%, first
Base acrylic acid selectivity 3.0%.
Embodiment 4
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 2030g deionization
In water, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O,
110g ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2It is molten that O puts into the nitric acid that 600g mass concentration is 3%
In liquid, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added in 30min molten
In liquid A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is obtained
Slurry a continues to heat slurry a under open state, until slurry a evaporates 1300ml water.Then slurry a is spray-dried,
When spray drying control inlet temperature be 250 DEG C, 120 DEG C of outlet temperature, and used in spray-drying process oxygen content for
The atmosphere of 6.5v%.Later, the powder of two ranges of resulting partial size 30-50um and 0.1-10um will be spray-dried according to matter
Amount in 20:1 mixing than being coated on porous inert porcelain ball (outer diameter 4.0mm, water absorption rate 15%), carrier and outer layer active component
Mass ratio is 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9Ni0.4Cs0.16Ox.Abrasion index is 0.3%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 385 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.5%, and methacrolein is selectively 86.8%, Methacrylic acid selectivity 2.2%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 387 DEG C, and isobutene conversion 99.7%, methacrolein is selectively 85.7%, first
Base acrylic acid selectivity 2.4%.
Embodiment 5
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 2030g deionization
In water, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O,
110g ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2It is molten that O puts into the nitric acid that 600g mass concentration is 3%
In liquid, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added in 30min molten
In liquid A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is obtained
Slurry a continues to heat slurry a under open state, until slurry a evaporates 1300ml water.Then slurry a is spray-dried,
When spray drying control inlet temperature be 250 DEG C, 120 DEG C of outlet temperature, and used in spray-drying process oxygen content for
The atmosphere of 14v%.Later, the powder of two ranges of resulting partial size 30-50um and 0.1-10um will be spray-dried according to matter
Amount in 20:1 mixing than being coated on porous inert porcelain ball (outer diameter 4.0mm, water absorption rate 15%), carrier and outer layer active component
Mass ratio is 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9Ni0.4Cs0.16Ox.Abrasion index is 0.3%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 391 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.6%, and methacrolein is selectively 86.1%, Methacrylic acid selectivity 1.8%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 393 DEG C, and isobutene conversion 99.7%, methacrolein is selectively 85.1%, first
Base acrylic acid selectivity 2.7%.
Embodiment 6
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 2030g deionization
In water, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O,
110g ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2It is molten that O puts into the nitric acid that 600g mass concentration is 3%
In liquid, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added in 30min molten
In liquid A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is obtained
Slurry a continues to heat slurry a under open state, until slurry a evaporates 1300ml water.Then slurry a is spray-dried,
When spray drying control inlet temperature be 250 DEG C, 120 DEG C of outlet temperature, and used in spray-drying process oxygen content for
The atmosphere of 10v%.Later, the powder of two ranges of resulting partial size 30-50um and 0.1-10um will be spray-dried according to matter
Amount in 20:1 mixing than being coated on porous inert porcelain ball (outer diameter 4.0mm, water absorption rate 15%), carrier and outer layer active component
Mass ratio is 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9Ni0.4Cs0.16Ox.Abrasion index is 0.3%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 383 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.5%, and methacrolein is selectively 86.1%, Methacrylic acid selectivity 1.8%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 387 DEG C, and isobutene conversion 99.6%, methacrolein is selectively 85.5%, first
Base acrylic acid selectivity 2.3%.
Comparative example 6
(1) preparation of catalyst
By 440g ammonium heptamolybdate (NH4)6Mo7O24.4H2O, 5.2g cesium carbonate Cs2CO3Put into 80 DEG C of 2030g deionization
In water, solution A is obtained after being completely dissolved.By 280g bismuth nitrate Bi (NO3)3·5H2O, 480g cobalt nitrate Co (NO3)2·6H2O,
110g ferric nitrate Fe (NO3)3·9H2O, 26g nickel nitrate Ni (NO3)2·6H2It is molten that O puts into the nitric acid that 600g mass concentration is 3%
In liquid, stirring is until obtain clear transparent solutions B；In the case where 80 DEG C of lasting stirrings, solution B is added in 30min molten
In liquid A, khaki slurry C is obtained, ammonium hydroxide is then added, control slurry pH value is about 2.5, after persistently stirring aging for 24 hours, is obtained
Slurry a continues to heat slurry a under open state, until slurry a evaporates 1300ml water.Then slurry a is spray-dried,
When spray drying control inlet temperature be 250 DEG C, 120 DEG C of outlet temperature, and in spray-drying process use air atmosphere.It
Afterwards, resulting partial size 30-50um will be spray-dried to mix according to mass ratio in 20:1 with the powder of two ranges of 0.1-10um
Coated in (outer diameter 4.0mm, water absorption rate 15%) on porous inert porcelain ball, the mass ratio of carrier and outer layer active component is 1.5:1.
Molding obtained above is placed in Muffle furnace in 550 DEG C of roasting 6h, 700g catalyst, catalyst composition are obtained
It is described as Mo according to each element the mass ratio of the material12Bi2.8Fe1.3Co7.9Ni0.4Cs0.16Ox.Abrasion index is 0.3%.
(2) reaction of isobutene Selective Oxidation methacrolein and methacrylic acid.
By 100mL Catalyst packing in internal diameter be 10mm fixed bed reactors in, using molar ratio as isobutene/oxygen/
Water/nitrogen=1/1.8/1.2/12.0 is raw material, air speed 1100h-1, salt temperature is 340 DEG C, and pressure (absolute pressure) is
The oxidation reaction of isobutene is carried out under the reaction condition of 0.13MPa, hot(test)-spot temperature is 401 DEG C after successive reaction 100h, isobutene
Conversion ratio is 99.1%, and methacrolein is selectively 84.5%, Methacrylic acid selectivity 1.5%, under this condition continuously
After reacting 4000h, hot(test)-spot temperature is 405 DEG C, and isobutene conversion 99.4%, methacrolein is selectively 81.3%, first
Base acrylic acid selectivity 2.1%.
Claims (11)
1. a kind of preparation method of more metal composite oxide catalysts, comprising the following steps:
(1) solution A containing molybdenum element and the solution B containing bismuth element are prepared；
(2) solution A and B are subjected to mixed precipitation, obtain slurry a；
(3) solid content of slurry a is adjusted by adjusting water content；
(4) the slurry a that drying steps (3) obtain, obtains catalyst precarsor；
(5) catalyst precarsor that step (4) obtains is formed, roasts, obtains catalyst；
Make 2~14:1 of mass ratio of its water and bismuth element in the step (3)；
The mass ratio of water and molybdenum element in the solution A is 3~40:1；
The mass ratio of water and bismuth element in the solution B is 1~22:1；
The step (4) carries out in the case where oxygen content is the atmosphere of 6~15v%.
2. the method according to claim 1, wherein the mass ratio of water and molybdenum element in the solution A be 6~
20:1.
3. the method according to claim 1, wherein the mass ratio of water and bismuth element in the solution B be 3~
15:1.
4. the method according to claim 1, wherein making the quality of its water and bismuth element in the step (3)
Than for 5~12:1.
5. method according to claim 1, which is characterized in that the step (4) is 7~12v%'s in oxygen content
It is carried out under atmosphere.
6. the method according to claim 1, wherein catalyst precarsor used when molding in the step (5)
Particle size range be 30-50 μm and 0.1-10 μm two kinds, the mass ratio of the two is 0.2~30:1.
7. the method according to claim 1, wherein catalyst precarsor used when molding in the step (5)
Particle size range be 30-50 μm and 0.1-10 μm two kinds, the mass ratio of the two is 0.5~20:1.
8. being roasted the method according to claim 1, wherein maturing temperature is 400~600 DEG C in the step (5)
The burning time is 2~10h.
9. the method according to claim 1, wherein maturing temperature is 450~550 DEG C in the step (5).
10. the catalyst prepared method according to claim 1 for unsaturated olefin prepare corresponding unsaturated aldehyde and/or
The purposes of unsaturated carboxylic acid, the unsaturated olefin include C5 or less unsaturated olefin.
11. purposes according to claim 10, which is characterized in that the unsaturated olefin is propylene and/or isobutene.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
| 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 |
| CN103769131A (en) * | 2012-10-23 | 2014-05-07 | 中国石油天然气股份有限公司 | Propylene selective oxidation catalyst and preparation method thereof |
| CN104781221A (en) * | 2012-11-07 | 2015-07-15 | 三菱丽阳株式会社 | Method for producing methacrolein and methacrylic acid |
| CN104998694A (en) * | 2015-05-29 | 2015-10-28 | 万华化学集团股份有限公司 | Cladding type catalyst carrier, preparation method thereof and cladding type catalyst |
| CN105555745A (en) * | 2013-07-18 | 2016-05-04 | 日本化药株式会社 | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
| 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 |
| CN103769131A (en) * | 2012-10-23 | 2014-05-07 | 中国石油天然气股份有限公司 | Propylene selective oxidation catalyst and preparation method thereof |
| CN104781221A (en) * | 2012-11-07 | 2015-07-15 | 三菱丽阳株式会社 | Method for producing methacrolein and methacrylic acid |
| CN105555745A (en) * | 2013-07-18 | 2016-05-04 | 日本化药株式会社 | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN104998694A (en) * | 2015-05-29 | 2015-10-28 | 万华化学集团股份有限公司 | Cladding type catalyst carrier, preparation method thereof and cladding type catalyst |
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