CN108325533A - Modified support, O composite metallic oxide catalyst and method for producing acrylic acid - Google Patents
Modified support, O composite metallic oxide catalyst and method for producing acrylic acid Download PDFInfo
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- CN108325533A CN108325533A CN201810102620.4A CN201810102620A CN108325533A CN 108325533 A CN108325533 A CN 108325533A CN 201810102620 A CN201810102620 A CN 201810102620A CN 108325533 A CN108325533 A CN 108325533A
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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
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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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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- 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
Abstract
The invention belongs to catalyst preparation technical fields, and in particular to a kind of modified support, O composite metallic oxide catalyst and method for producing acrylic acid.The modified support is that dipping absorption has Mo on a kind of inert carrier12VaAbBcCdDeEfFgOnThe metal composite oxide of general formula, the catalyst are that coating has Mo on the modified support surface12VaAbBcCdDeEfFgOnThe metal composite oxide of general formula.The molybdenum vanadium catalyst that the catalyst of the present invention is more conventional is compared, with more active catalyst sites, catalyst activity higher, simultaneously, invention also reduces the concentration of catalyst local reaction active site, effectively prevent catalyst in the possibility for being locally generated big calorimetric, greatly suppress the sublimation of molybdenum element in catalyst to a certain extent, the activity for stabilizing catalyst extends the service life of catalyst.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of modified support, composite metal oxide catalyst
Agent and method for producing acrylic acid.
Background technology
In recent years, the exploitation of oil and natural gas has driven the rapid development of fine chemistry industry, and acrylicacidandesters are as weight
One of fine chemical material wanted is widely used in coating, building materials, adhesive, weaving, leather, papermaking, oil recovery and water process etc.
Field.With industrial expansions such as building, electronics, automobiles, the demand and production capacity of acrylic acid are continuously increased.
Currently, the mainstream technology route of acrylic acid production is still the industrialized propylene two-step method selection of last century the seventies
Methacrylaldehyde generates acrylic acid by further selective oxidation after oxidation technology, i.e. propylene fraction are oxidized to methacrylaldehyde.In order to constantly excellent
Change reaction process, obtain higher acrylic acid yield, the catalyst that a large amount of catalytic oxidation propylene aldehyde generate acrylic acid is constantly opened
Hair application, such as molybdenum-vanadium (Mo-V) class composite oxidant.However, the reaction that catalytic oxidation propylene aldehyde prepares acrylic acid is one strong
Exothermic reaction generally uses calandria type fixed bed reactor, in calandria type fixed bed reactor to meet the requirement of heat transfer
Each tubulation relative tubular diameter is smaller, and heat transfer specific surface area is very big, in addition high-speed, short residence time, and filling is urged again in tubulation
Agent, the back-mixing situation very little of logistics, that is to say, that whole Thermal feedback very little, if the amount of heat released in reaction process is not
It can remove in time, just will produce the overtemperature of catalyst bed part, is i.e. " hot spot "." hot spot " is emerged, and portion on the one hand can be caused
Divide propylene feedstocks excessive oxidation, the selectivity of reaction is caused to decline, the amount of target product acrylic acid is reduced, and the pairs such as oxycarbide
Product dramatically increases；The distillation of molybdenum, causes the damage of catalyst, influences the use of catalyst in another aspect meeting accelerator activator
Service life.Meanwhile the molybdenum of volatilization is assembled on " hot spot " nearby tube wall, so that reaction bed pressure drop is increased, increases the energy consumption of device.Cause
This, stringent controlling reaction temperature inhibits the generation of " hot spot " as far as possible, for improving the yield of target product acrylic acid, extending
The service life of catalyst and the energy consumption for reducing device, there is vital effect.
To solve the problems, such as " hot spot " present in catalytic oxidation, there are many technological means to be applied.Such as：1)
Catalyst bed is divided into multiple sections, each section uses the catalyst of different inert substance dilution ratio；2) prolong gas stream
Dynamic direction changes catalyst load factor；3) varigrained catalyst, i.e., from gas access to exit, the catalysis of filling are loaded
Agent granularity is gradually reduced；4) addition alkali or alkaline earth metal is to reduce the activity of catalyst bed inlet catalyst.
Although can inhibit " hot spot " to a certain extent, " hot spot " still remains the above method.In addition, because increasing
The dilution ratio of big inert substance or the load factor or the varigrained catalyst of filling for reducing catalyst activity component, are all drops
At low catalyst bed inlet in catalyst active material content, that is, change the activity of catalyst on catalyst bed direction,
And the thermal stability of catalyst is not improved, and the catalyst of inlet is easier to inactivate compared with the catalyst in exit, with
The extension of the cycle of operation, the selectivity and yield of acrylic acid can be also greatly reduced.Therefore, the above method cannot be solved fundamentally
Catalytic oxidation propylene aldehyde produces the problem of selectivity and catalyst life of acrylic acid.
Invention content
Therefore, the technical problem to be solved in the present invention is to overcome existing catalyst cannot long-term efficiently catalyzing and oxidizing third
Olefine aldehydr produces the problem of acrylic acid, to provide a kind of power not changing catalyst activity on catalyst bed direction, even if
The catalyst that long-term efficiently catalytic oxidation propylene aldehyde produces acrylic acid is remained under the conditions of " hot spot " is existing.Meanwhile this hair
It is bright to additionally provide the modified support produced used in the catalyst, and provide a kind of production acrylic acid.
In order to solve the above technical problems, the present invention provides a kind of modified support, the modified support includes carrier and leaching
Stain is adsorbed in the metal composite oxide indicated by general formula (I) on the carrier：
Mo12VaAbBcCdDeEfFgOn (Ⅰ)
Wherein：
A is selected from least one of W, Nb, Ta, Cr, Ce；
B is selected from least one of Cu, Ni, Co, Fe, Mn, Zn；
C is selected from least one of Sb, Te or Bi；
D is selected from least one of alkali metal；
E is selected from least one of alkaline-earth metal；
F is selected from least one of Si, Al, Ti or Zr；
The value range of a is 1~6；
The value range of b is 0.2~4；
The value range of c is 0.5~6；
The value range of d is 0~2；
The value range of e is 0~1；
The value range of f is 0~1；
The value range of g is 0~6；
N is the oxygen atom sum met needed for other element valences.
Further, in terms of the gross mass of carrier, the load factor of the metal composite oxide is 1~20%, preferably 3
~18%, more preferably 5~15%.Wherein：Load factor=(1- inert carriers quality/modified support quality) × 100%.
Further, the carrier is selected from aluminium oxide, silica, titanium dioxide, magnesia, zirconium oxide, silica-
At least one of aluminium oxide, silica-alumina, silicon carbide, silicon nitride, diatomite, zeolite.
Further, the carrier is aluminium oxide.
Further, the shape of the carrier is annular, spherical shape, cylinder, cloverleaf pattern, hollow cylindrical or bar shaped,
It is preferably spherical.Spherical shape does not need sphere, as long as substantially similar spherical.
Further, a diameter of 2~10mm, preferably 3~8mm, more preferably 4~6mm of the spherical shape.
The present invention also provides the preparation methods of above-mentioned modified support, including：
(1) slurries containing required metal ion are prepared；
(2) by carrier impregnation slurries described in step (1), dry, roasting molding obtains the modified support.
Further, the temperature roasted described in step (1) is 300~800 DEG C, and the time is 1~10 hour；Preferably,
The temperature of the roasting is 400~600 DEG C, and the time is 2~8 hours；More electedly, the temperature of the roasting is 450~550
DEG C, the time is 3~6 hours.
Concentration of slurry can make corresponding adjustment according to actual needs in step (1).Specifically, in step (1), slurry
Coprecipitation reaction is carried out by each element component compound dissolving mixing for being related to metal composite oxide when the preparation of liquid, altogether
Random time point after precipitation stops heating, you can to obtain the slurry of various concentration.Prepare the slurry needed for modified support
The water absorption rate of the inert carrier that the amount of liquid depends on itself.
The present invention also provides a kind of O composite metallic oxide catalyst, including above-mentioned modified support or according to above-mentioned side
The modified support that method is prepared and the metal composite oxide with general formula shown in formula (I) being supported on the carrier.
Further, in terms of the gross mass of modified support, the load factor of the metal composite oxide is 10%~60%,
Preferably 20~50%, more preferably 25~40%.Wherein：Load factor=(1- modified supports quality/catalyst quality) ×
100%.
The intensity of catalyst is one of important parameter of its performance, prepared by O composite metallic oxide catalyst of the invention
Intensity enhancing auxiliary agent can also be added in the process, such as：Cellulose, methylcellulose, inorfil, glass fibre, graphite, poly- third
Alkene, polyvinyl alcohol etc..In addition, the O composite metallic oxide catalyst of the present invention can also add molding in coating molding and help
Agent, such as：Water, ethyl alcohol, ethylene glycol, glycerine, propionic acid, propyl alcohol, maleic acid, nitric acid, ammonium nitrate, Ludox, Aluminum sol etc., it is preferably sweet
Oil.
The present invention also provides the preparation methods of above-mentioned O composite metallic oxide catalyst, including：
(1) slurries containing required metal ion are prepared；
(2) slurries described in step (1) are evaporated, are carried on the modified support surface, dry, roasting obtains described multiple
Close metal oxide catalyst.
Further, the temperature roasted described in step (2) is 300~420 DEG C, and the time is 1~10 hour；Preferred institute
The temperature of roasting is stated to be 350 DEG C~400 DEG C, the time is 2~8 hours；The temperature of the preferred roasting is 360~390
DEG C, the time is 3~7 hours.
The method loaded in step (2) may be used conventional method and carry out, such as：Extrusion or coating method.From technique
Convenience is set out, and the metal composite oxide ingredient is supported on the surface of modified support by the mode being preferably coated with.Preferably,
Described to be applied to centrifugal flow coating, the rotating speed of control centrifugation coating machine is 20~35rpm when coating, described compound to ensure
Metal oxide component is more uniformly coated in modified support surface.
The present invention also provides a kind of production acrylic acid, using above-mentioned O composite metallic oxide catalyst or according to
O composite metallic oxide catalyst catalytic oxidation propylene aldehyde prepared by above-mentioned preparation method produces acrylic acid.The catalysis oxidation is
Under the conditions of existing for molecular oxygen or molecule-containing keto, by using above-mentioned O composite metallic oxide catalyst catalytic oxidation propylene aldehyde
Or the gas containing methacrylaldehyde, obtain acrylic acid.That is, other than using this restrictive condition of the catalyst of the present invention,
Without others restrictive condition, such as：Catalysis reaction can general device (such as fixed bed reactors, fluidized-bed reactor or
Moving-burden bed reactor) in carry out.
Reactor feed gas is not particularly limited in production acrylic acid provided by the present invention, can be methacrylaldehyde,
The gaseous mixture of molecular oxygen and inert gas composition, can also be by the obtained propylene aldehyde product gas of propylene catalysis oxidation.When with
When the gaseous mixture of methacrylaldehyde, molecular oxygen and inert gas composition is as unstripped gas, the proportional region respectively formed in unstripped gas is：1
~15% methacrylaldehyde, preferably 3~13%, 0.5~28% oxygen, preferably 3~20%, 0~30% vapor, preferably
The inert gases such as 0~20% and 30~80% nitrogen, preferably 40~70%.The technique used for：Reaction temperature 220
~300 DEG C, preferably 240~260 DEG C, 0.01~0.2MPa of pressure, 500~1700h of air speed-1, tube inner diameter 26.6mm, instead
Answer length of tube 3500mm.
Technical scheme of the present invention has the following advantages that：
1. a kind of modified support provided by the invention, the modified support is in the specific composition metal oxygen of supported on carriers
Compound loads specific metal composite oxide in the inside of inert carrier, is provided more for subsequent catalytic oxidation
Active site, being smoothed out to provide and effectively ensure for catalytic oxidation.Compared with the prior art modified support or do not change
Property carrier compare, the active higher of catalyst being prepared by the modified support of the present invention is more advantageous to catalysis oxidation third
Olefine aldehydr prepares acrylic acid.
2. a kind of modified support provided by the invention, further defines the load factor of the metal composite oxide, both
Good modified effect is reached, has in turn avoided causing methacrylaldehyde because of the excessive metal composite oxide active component of carrier adsorption
Reaction raw materials reduce the problem of the selectivity of catalyst in carrier inside generation carbon oxides as by-products.
3. a kind of modified support provided by the invention, selects aluminium oxide as inert carrier, flourishing hole construction makes
It obtains reactant to be easy to adsorb, reaction product is easy to be desorbed, and effectively inhibits the generation of deep oxidation side reaction.
4. a kind of modified support provided by the invention further defines the shape and grain size of carrier, improves catalyst
Reactivity.
5. O composite metallic oxide catalyst provided by the invention is to contain molybdenum and vanadium in the modified support area load
Metal composite oxide, and further define the metal composite oxide to the load factor of modified support, improve and urge
The reactivity and selectivity of agent.
6. the preparation method of O composite metallic oxide catalyst provided by the invention, this method is first to prepare modified support,
Then the O composite metallic oxide catalyst is prepared again.Because inert carrier has porous structure, leaching when modified support is prepared
Stain absorption can make attached catalyst active component inside inert carrier, increase the active site of catalysis reaction, improve catalyst
Activity is conducive to being smoothed out for catalysis reaction.At the same time it can also reduce the concentration of catalyst local reaction active site, have
Effect avoids catalyst in the possibility for being locally generated big calorimetric, greatly suppresses the distillation of molybdenum element in catalyst to a certain extent
It is lost in, stabilizes the activity of catalyst, extend the service life of catalyst.It is also diluted in addition, two-step method prepares catalyst
The active site of catalyst local reaction, it is suppressed that the generation of side reaction improves the selectivity of main reaction acrylic acid.
7. production acrylic acid provided by the invention, this method is the condition existing for molecular oxygen or molecule-containing keto
Under, prepare acrylic acid using the O composite metallic oxide catalyst catalytic oxidation propylene aldehyde.In 245 DEG C of reaction temperature, pressure
0.05MPa, air speed 1700h-1, under conditions of tube inner diameter 26.6mm, tube length of reaction tube 3500mm, the yield of acrylic acid is reachable
96.8%, the selectivity of acrylic acid achieves preferable technique effect up to 97.5%, can push away on a large scale in the industrial production
Wide application.
Specific implementation mode
Technical scheme of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
There is the every other embodiment obtained under the premise of making creative work, shall fall within the protection scope of the present invention.In addition, below
Involved technical characteristic as long as they do not conflict with each other can be mutual in described different embodiments of the present invention
In conjunction with.
In embodiments given below, the investigation evaluation condition to catalyst is：
Reactor：Stainless steel reaction pipe, internal diameter 26.6mm, length 3500mm
Catalyst filling amount：1500mL
Raw material ratio：Methacrylaldehyde/oxygen/water steam/nitrogen=5/5.5/25/64.5
Reaction velocity：1700h-1
Acrolein conversion rate, acrylic acid yield and selective computational methods are：
Acrolein conversion rate (%)=(methacrylaldehyde molal quantity in methacrylaldehyde molal quantity/raw material of reaction) × 100%
Acrylic acid yield (%)=(methacrylaldehyde molal quantity in acrylic acid molal quantity/raw material of generation) × 100%
Acrylic acid selectivity (%)=(the methacrylaldehyde molal quantity of acrylic acid molal quantity/reaction of generation) × 100%
Present disclosure is further elaborated below by embodiment.
Embodiment 1
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 44.3g ammonium paratungstates, 96.7g ammonium metavanadates, 1.91g nitre thereto
Sour potassium, 7.6g cesium nitrates, stirring are added 300mL deionized waters, heated in another container to being completely dissolved to obtain solution A
Under stirring condition, 91.7g copper nitrates, 10.2g antimony oxides and 37.7g titanium dioxide is added, solution B is obtained, by solution B
It is added drop-wise in solution A, obtains slurries C.270mL slurries C are taken out, by 1500g inert aluminas carrier impregnation in slurries C, are done
Dry, 450 DEG C of roastings obtain modified support in 5 hours.Remaining slurries C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh
Particle, is carried on modified support surface by the way of centrifugal flow coating, and 390 DEG C of roastings obtain the compound gold in 4 hours
Belong to oxide catalyst finished product, other than oxygen, the group of the metal composite oxide becomes
Mo12V3.5Cu1.6W0.7Sb0.6K0.08Sr0.23Ti2.0。
In the present embodiment, the metal composite oxide is 10% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 32%.
Embodiment 2
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 95g ammonium paratungstates, 96.7g ammonium metavanadates, 3.6g nitric acid thereto
300mL deionized waters are added to being completely dissolved to obtain solution A in potassium, 13.9g strontium nitrates, stirring in another container, in heating and
Under stirring condition, 137.6g copper nitrates, 13.6g antimony oxides and 75.4g titanium dioxide is added, solution B is obtained, by solution B
It is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 2 hours, takes out 270mL slurries C, will
1500g inert aluminas carrier impregnation is dry in slurries C, and 550 DEG C of roastings obtain modified support in 6 hours.By remaining slurries
C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified support is carried on by the way of centrifugal flow coating
Surface, 360 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 4 hours, other than oxygen, the composition metal oxygen
The group of compound becomes Mo12V3.5Cu2.4W1.5Sb0.8K0.15Sr0.42Ti4.0。
In the present embodiment, the metal composite oxide is 15% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 30%.
Embodiment 3
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 114g ammonium paratungstates, 96.7g ammonium metavanadates, 5.7g nitric acid thereto
300mL deionized waters are added to being completely dissolved to obtain solution A in potassium, 21.8g strontium nitrates, stirring in another container, in heating and
Under stirring condition, 183.5g copper nitrates, 20.4g antimony oxides and 113g titanium dioxide is added, obtains solution B, solution B is dripped
It is added in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 30 minutes, takes out 270mL slurries C, will
1500g inert aluminas carrier impregnation is dry in slurries C, and 500 DEG C of roastings obtain modified support in 5 hours.By remaining slurries
C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified support is carried on by the way of centrifugal flow coating
Surface, 380 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 6 hours, other than oxygen, the composition metal oxygen
The group of compound becomes Mo12V3.5Cu3.2W1.8Sb1.2K0.24Sr0.66Ti6.0。
In the present embodiment, the metal composite oxide is 5% to the load factor of the carrier of inert alumina, to modified oxygen
The load factor for changing alumina supporter is 40%.
Embodiment 4
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 44.3g ammonium paratungstates, 110.5g ammonium metavanadates, 3.6g nitre thereto
Sour potassium, 10.9g strontium nitrates, 16.3g magnesium nitrates, stirring are added 300mL and gone in another container to being completely dissolved to obtain solution A
Ionized water is heating under stirring condition, 91.7g copper nitrates, 13.6g antimony oxides and 113g titanium dioxide is added, obtains
Solution B is added drop-wise in solution A by solution B, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 1 hour, takes out
270mL slurries C, dry by 1500g inert aluminas carrier impregnation in slurries C, 550 DEG C of roastings obtain modified load for 3 hours
Body.Remaining slurries C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, using the side of centrifugal flow coating
Formula is carried on modified support surface, and 390 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 4 hours, in addition to oxygen with
Outside, the group of the metal composite oxide becomes Mo12V4.0Cu1.6W0.7Sb0.8K0.15Sr0.33Mg0.27Ti6.0。
In the present embodiment, the metal composite oxide is 8% to the load factor of the carrier of inert alumina, to modified oxygen
The load factor for changing alumina supporter is 35%.
Embodiment 5
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 95g ammonium paratungstates, 110.5g ammonium metavanadates, 5.7g nitric acid thereto
300mL deionizations are added to being completely dissolved to obtain solution A in potassium, 4g strontium nitrates and 5.5g magnesium nitrates, stirring in another container
Water is heating under stirring condition, 68.8g copper nitrates, 110g cobalt nitrates, 20.4g antimony oxides, 28.3 titanium dioxide is added
With 37.7g titanium dioxide, solution B is obtained, solution B is added drop-wise in solution A, obtains slurries C.270mL slurries C are taken out, it will
1500g inert aluminas carrier impregnation is dry in slurries C, and 550 DEG C of roastings obtain modified support in 6 hours.By remaining slurries
C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified support is carried on by the way of centrifugal flow coating
Surface, 370 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 7 hours, other than oxygen, the composition metal oxygen
The group of compound becomes Mo12V4.0Cu1.2Co1.6W1.5Sb1.2K0.24Sr0.12Mg0.09Ti2.0。
In the present embodiment, the metal composite oxide is 7% to the load factor of the carrier of inert alumina, to modified oxygen
The load factor for changing alumina supporter is 32%.
Embodiment 6
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 114g ammonium paratungstates, 110.5g ammonium metavanadate 1.9g nitric acid thereto
300mL deionized waters are added to being completely dissolved to obtain solution A in potassium, 13.9g strontium nitrates, stirring in another container, in heating and
Under stirring condition, 183.5g copper nitrates, 10.2g antimony oxides and 75.4g titanium dioxide is added, solution B is obtained, by solution B
It is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 2 hours, takes out 270mL slurries C, will
1500g inert aluminas carrier impregnation is dry in slurries C, and 500 DEG C of roastings obtain modified support in 5 hours.By remaining slurries
C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified support is carried on by the way of centrifugal flow coating
Surface, 380 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 5 hours, other than oxygen, the composition metal oxygen
The group of compound becomes Mo12V4.0Cu3.2W1.8Sb0.6K0.08Sr0.42Ti4.0。
In the present embodiment, the metal composite oxide is 14% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 35%.
Embodiment 7
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 95g ammonium paratungstates, 143.7g ammonium metavanadates, 5.7g nitric acid thereto
300mL deionized waters are added to being completely dissolved to obtain solution A in potassium, 13.9g strontium nitrates, stirring in another container, in heating and
Under stirring condition, 91.7g copper nitrates, 5.1g antimony oxides, 18.8g tellurium dioxide and 113g titanium dioxide is added, obtains molten
Liquid B, solution B is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 1 hour, takes out 270mL
Slurries C, by 1500g inert aluminas carrier impregnation in slurries C, dry, 450 DEG C of roastings obtain modified support in 6 hours.It will be remaining
Solution C be evaporated to dry, 120 DEG C of drying and are ground into 80 mesh particles, are carried on and are changed by the way of centrifugal flow coating
Property carrier surface, 390 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 3 hours, described compound other than oxygen
The group of metal oxide becomes Mo12V5.2Cu1.6W1.5Sb0.3Te0.5K0.24Sr0.42Ti6.0。
In the present embodiment, the metal composite oxide is 6% to the load factor of the carrier of inert alumina, to modified oxygen
The load factor for changing alumina supporter is 38%.
Embodiment 8
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 62.7g niobium pentaoxides, 143.7g ammonium metavanadates, 1.9g thereto
Potassium nitrate, 53g barium nitrates, stirring are added 300mL deionized waters, heated in another container to being completely dissolved to obtain solution A
Under stirring condition, 137.6g copper nitrates, 13.6g antimony oxides and 37.7g titanium dioxide is added, solution B is obtained, by solution
B is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 1 hour, takes out 270mL slurries C, will
1500g inert aluminas carrier impregnation is dry in slurries C, and 800 DEG C of roastings obtain modified support in 1 hour.By remaining slurries
C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified support is carried on by the way of centrifugal flow coating
Surface, 420 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 1 hour, other than oxygen, the composition metal oxygen
The group of compound becomes Mo12V5.2Cu2.4Nb2.0Sb0.8K0.08Ba0.86Ti2.0。
In the present embodiment, the metal composite oxide is 12% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 30%.
Embodiment 9
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 44.3g ammonium paratungstates, 143.7g ammonium metavanadates, 3.6g nitre thereto
Sour potassium, 4.0g strontium nitrates, 9.9g barium nitrates, stirring to being completely dissolved to obtain solution A, be added in another container 300mL go from
Sub- water is heating under stirring condition, 183.5g copper nitrates, 20.4g antimony oxides and 75.4g titanium dioxide is added, obtains
Solution B is added drop-wise in solution A by solution B, obtains slurries C.100 DEG C are warming up to, constant temperature 2 hours takes out 270mL slurries C, will
1500g inert aluminas carrier impregnation is dry in slurries C, and 300 DEG C of roastings obtain modified support in 10 hours.By remaining slurry
Liquid C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified load is carried on by the way of centrifugal flow coating
Body surface face, 300 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 10 hours, other than oxygen, the compound gold
Belonging to the group of oxide becomes Mo12V5.2Cu3.2W0.7Sb1.2K0.15Sr0.12Ba0.16Ti4.0。
In the present embodiment, the metal composite oxide is 15% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 26%.
Embodiment 10
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 114g ammonium paratungstates, 96.7g ammonium metavanadates, 3.6g nitric acid thereto
300mL deionized waters are added to being completely dissolved to obtain solution A in potassium, 13.9g strontium nitrates, stirring in another container, in heating and
Under stirring condition, 90.6g nickel nitrates, 20.4g antimony oxides and 23.3g zirconium dioxides is added, obtains solution B, solution B is dripped
It is added in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 30 minutes, takes out 270mL slurries C, will
1500g inert aluminas carrier impregnation is dry in slurries C, and 500 DEG C of roastings obtain modified support in 5 hours.By remaining slurries
C be evaporated to it is dry, 120 DEG C drying, be ground into 80 mesh particles, modified support table be carried on by the way of centrifugal flow coating
Face, 390 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 5 hours, other than oxygen, the composition metal oxidation
The group of object becomes Mo12V3.5Ni1.32W1.8Sb1.2K0.15Sr0.42Zr0.8。
In the present embodiment, the metal composite oxide is 10% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 35%.
Embodiment 11
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 22.2g ammonium paratungstates, 17.3g niobium pentaoxides, 96.7g thereto
300mL is added to being completely dissolved to obtain solution A in ammonium metavanadate, 5.7g potassium nitrate, 21.8g strontium nitrates, stirring in another container
Deionized water is heating under stirring condition, 68.8g copper nitrates, 75.5g nickel nitrates, 10.2g antimony oxides, 37.7g is added
Titanium dioxide and 23.3g zirconium dioxides, obtain solution B, solution B are added drop-wise in solution A, obtain slurries C.100 DEG C are warming up to,
After constant temperature 1 hour, stop heating, takes out 270mL slurries C, it is dry by 1500g inert aluminas carrier impregnation in slurries C,
500 DEG C of roastings obtain modified support in 5 hours.Remaining solution C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh
Grain, is carried on modified support surface by the way of centrifugal flow coating, and 370 DEG C of roastings obtain the composition metal in 5 hours
Oxide catalyst finished product, other than oxygen, the group of the metal composite oxide becomes
Mo12V3.5Cu1.2Ni1.1W0.35Nb0.55Sb0.6K0.24Sr0.66Ti2.0Zr0.8。
In the present embodiment, the metal composite oxide is 8% to the load factor of the carrier of inert alumina, to modified oxygen
The load factor for changing alumina supporter is 36%.
Embodiment 12
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 95g ammonium paratungstates, 96.7g ammonium metavanadates, 1.9g nitric acid thereto
Potassium and 19.7g barium nitrates, stirring are added 300mL deionized waters, heated in another container to being completely dissolved to obtain solution A
Under stirring condition, 330g cobalt nitrates, 13.6g antimony oxides and 113g titanium dioxide is added, obtains solution B, solution B is dripped
It is added in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 1 hour, takes out 270mL slurries C, takes 1500g
Inert alumina carrier impregnation is dry in slurries C, and 500 DEG C of roastings obtain modified support in 5 hours.Remaining slurries C is evaporated
To dry, 120 DEG C of drying, and 80 mesh particles are ground into, modified support surface are carried on by the way of centrifugal flow coating,
390 DEG C of roastings obtain the O composite metallic oxide catalyst finished product, other than oxygen, the metal composite oxide in 5 hours
Group become Mo12V3.5Co4.8W1.5Sb0.8K0.08Ba0.32Ti6.0。
In the present embodiment, the metal composite oxide is 10% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 38%.
Embodiment 13
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 95g ammonium paratungstates, 110.5g ammonium metavanadates, 1.9g nitric acid thereto
Potassium and 21.8g strontium nitrates, stirring are added 300mL deionized waters, heated in another container to being completely dissolved to obtain solution A
Under stirring condition, 164.9g cobalt nitrates, 67.8g tellurium dioxide and 75.4g titanium dioxide is added, solution B is obtained, by solution B
It is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 2 hours, takes out 270mL slurries C, takes
1500g inert aluminas carrier impregnation is dry in slurries C, and 500 DEG C of roastings obtain modified support in 5 hours.By remaining slurries
C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified support is carried on by the way of centrifugal flow coating
Surface, 390 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 5 hours, other than oxygen, the composition metal oxygen
The group of compound becomes Mo12V4.0Co2.4W1.5Te1.8K0.08Sr0.66Ti4.0。
In the present embodiment, the metal composite oxide is 15% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 28%.
Embodiment 14
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 113.9g ammonium paratungstates, 110.5g ammonium metavanadates, 8.3g thereto
300mL deionized waters are added to being completely dissolved to obtain solution A in cesium nitrate and 10.9g magnesium nitrates, stirring in another container,
Under heating and stirring condition, 137.6g copper nitrates, 33.9g tellurium dioxide and 113g titanium dioxide is added, obtains solution B, it will be molten
Liquid B is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 1 hour, takes out 270mL slurries C, takes
1500g inert aluminas carrier impregnation is dry in slurries C, and 500 DEG C of roastings obtain modified support in 5 hours.By remaining slurries
C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified support is carried on by the way of centrifugal flow coating
Surface, 380 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 6 hours, other than oxygen, the composition metal oxygen
The group of compound becomes Mo12V4.0Cu2.4W1.8Te0.9Cs0.18Mg0.18Ti6.0。
In the present embodiment, the metal composite oxide is 12% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 26%.
Embodiment 15
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 34.5g niobium pentaoxides, 110.5g ammonium metavanadates, 5.7g thereto
300mL deionized waters are added to being completely dissolved to obtain solution A in potassium nitrate and 13.9g strontium nitrates, stirring in another container,
Under heating and stirring condition, 192.2g nickel nitrates, 13.6g antimony oxides, 18.9g titanium dioxide and 11.6g titanium dioxides is added
Zirconium obtains solution B, and solution B is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops adding after 0.5 hour
Heat takes out 270mL slurries C, takes 1500g inert aluminas carrier impregnation in slurries C, dry, and 500 DEG C of roastings obtain for 5 hours
Modified support.Remaining slurries C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, is applied using centrifugal flowing
The mode covered is carried on modified support surface, and 390 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 6 hours, remove
Other than oxygen, the group of the metal composite oxide becomes Mo12V4.0Ni2.8Nb1.1Sb0.8K0.24Sr0.42Ti1.0Zr0.4。
In the present embodiment, the metal composite oxide is 8% to the load factor of the carrier of inert alumina, to modified oxygen
The load factor for changing alumina supporter is 38%.
Embodiment 16
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 113.9g ammonium paratungstates, 143.7g ammonium metavanadates, 12.9g thereto
Cesium nitrate and 7.6g strontium nitrates, stirring are added 300mL deionized waters, added in another container to being completely dissolved to obtain solution A
Under heat and stirring condition, 45.9g copper nitrates, 45.3g nickel nitrates, 13.6g antimony oxides and 75.4g titanium dioxide is added, obtains
To solution B, solution B is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating, take after 0.5 hour
Go out 270mL slurries C, take 1500g inert aluminas carrier impregnation in slurries C, dry, 500 DEG C of roastings obtain modified load for 5 hours
Body.Remaining slurries C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, using the side of centrifugal flow coating
Formula is carried on modified support surface, and 380 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 6 hours, in addition to oxygen with
Outside, the group of the metal composite oxide becomes Mo12V5.2Cu0.8Ni0.66W1.8Sb0.8Cs0.28Sr0.23Ti4.0。
In the present embodiment, the metal composite oxide is 6% to the load factor of the carrier of inert alumina, to modified oxygen
The load factor for changing alumina supporter is 39%.
Embodiment 17
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 44.3g ammonium paratungstates, 143.7g ammonium metavanadates, 0.95g thereto
300mL is added to being completely dissolved to obtain solution A in potassium nitrate, 2.8g cesium nitrates and 13.9g strontium nitrates, stirring in another container
Deionized water is heating under stirring condition, 137.6g copper nitrates, 20.4g antimony oxides and 113g titanium dioxide is added, obtains
To solution B, solution B is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 2 hours, takes out
270mL slurries C, take 1500g inert aluminas carrier impregnation in slurries C, dry, and 500 DEG C of roastings obtain modified load for 5 hours
Body.Remaining slurries C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, using the side of centrifugal flow coating
Formula is carried on modified support surface, and 370 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 3 hours, in addition to oxygen with
Outside, the group of the metal composite oxide becomes Mo12V5.2Cu2.4W0.7Sb1.2K0.04Cs0.06Sr0.42Ti6.0。
In the present embodiment, the metal composite oxide is 15% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 27%.
Embodiment 18
A kind of O composite metallic oxide catalyst is present embodiments provided, preparation method is specially：By 1500mL go from
Sub- water is heated to 80 DEG C, is separately added into 500g ammonium paramolybdates, 95g ammonium paratungstates, 143.7g ammonium metavanadates, 3.6g nitric acid thereto
Potassium and 21.8g strontium nitrates, stirring are added 300mL deionized waters, heated in another container to being completely dissolved to obtain solution A
Under stirring condition, 183.5g copper nitrates, 10.2g antimony oxides and 37.7g titanium dioxide is added, solution B is obtained, by solution
B is added drop-wise in solution A, obtains slurries C.100 DEG C are warming up to, constant temperature stops heating after 1 hour, takes out 270mL slurries C, takes
1500g inert aluminas carrier impregnation is dry in slurries C, and 500 DEG C of roastings obtain modified support in 5 hours.By remaining slurries
C is evaporated to dry, 120 DEG C of drying, and is ground into 80 mesh particles, and modified support is carried on by the way of centrifugal flow coating
Surface, 380 DEG C of roastings obtain the O composite metallic oxide catalyst finished product in 4 hours, other than oxygen, the composition metal oxygen
The group of compound becomes Mo12V5.2Cu3.2W1.5Sb0.6K0.15Sr0.66Ti2.0。
In the present embodiment, the metal composite oxide is 10% to the load factor of the carrier of inert alumina, to modification
The load factor of alumina support is 36%.
Comparative example 1
This comparative example provides a kind of O composite metallic oxide catalyst, ingredient with embodiment 1, the difference is that,
The O composite metallic oxide catalyst of this comparative example is prepared using one-step method, i.e., is directly evaporated slurries C, is then coated in not changing
The inert alumina surface of property, the ingredient of the metal composite oxide is the same as embodiment 1.
Comparative example 2
This comparative example provides a kind of O composite metallic oxide catalyst, and with embodiment 1, difference exists preparation method
In modified support is that inert alumina carrier is modified processing, concrete operations with Ti-Si-O oxides in this comparative example
For：
Tetra- titanium oxide of 188g is added in 1000mL ice water, it is strong to stir, 20% Ludox 100g is added, stirring is equal
It is even.The alumina support that 1500g average diameters are 4.5mm is positioned in above-mentioned mixed solution, maintenance 1 is small at a temperature of 80 DEG C
When, then take out drying.Then 500 DEG C of roasting temperatures 30 minutes are down to room temperature, obtaining load has general formula Ti0.99SiOxIt indicates
Metal composite oxide surface modified carrier.In terms of inert alumina carrier, the load factor of metal composite oxide is
39%.
Comparative example 3
This comparative example provides a kind of O composite metallic oxide catalyst, ingredient and the preparation method is the same as that of Example 1, different
Place is, in terms of the gross mass of inert alumina, the load factor of metal composite oxide described in this comparative example is 25%,
Ingredient is the same as embodiment 1.
Experimental example
Catalyst obtained in embodiment 1-18 and comparative example 1-3 is subjected to investigation evaluation respectively under different conditions,
Evaluation results are shown in Table 1.
The single tube evaluation experimental data of 1 catalyst of table
As can be seen from the above table, the catalyst performance of 1-18 of the embodiment of the present invention is substantially better than the catalyst of comparative example 1-3
Performance produces acrylic acid using the O composite metallic oxide catalyst catalytic oxidation propylene aldehyde of the present invention, achieves preferable skill
Art effect.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (11)
1. a kind of modified support, which is characterized in that be adsorbed on the carrier including carrier and dipping and indicated by general formula (I)
Metal composite oxide：
Mo12VaAbBcCdDeEfFgOn (Ⅰ)
Wherein：
A is selected from least one of W, Nb, Ta, Cr, Ce；
B is selected from least one of Cu, Ni, Co, Fe, Mn, Zn；
C is selected from least one of Sb, Te, Bi；
D is selected from least one of alkali metal；
E is selected from least one of alkaline-earth metal；
F is selected from least one of Si, Al, Ti, Zr；
The value range of a is 1~6；
The value range of b is 0.2~4；
The value range of c is 0.5~6；
The value range of d is 0~2；
The value range of e is 0~1；
The value range of f is 0~1；
The value range of g is 0~6；
N is the oxygen atom sum met needed for other element valences.
2. modified support according to claim 1, which is characterized in that in terms of the gross mass of carrier, the composition metal oxygen
The load factor of compound is 1~20%, preferably 3~18%, more preferably 5~15%.
3. modified support according to claim 1 or 2, which is characterized in that the carrier be selected from aluminium oxide, silica,
Titanium dioxide, magnesia, zirconium oxide, silica-alumina, silica-alumina, silicon carbide, silicon nitride, diatomite,
At least one of zeolite.
4. modified support according to claim 3, which is characterized in that the carrier is aluminium oxide.
5. according to the preparation method of claim 1-4 any one of them modified supports, which is characterized in that including：
(1) slurries containing required metal ion are prepared；
(2) by carrier impregnation slurries described in step (1), dry, roasting molding obtains the modified support.
6. the preparation method of modified support according to claim 5, which is characterized in that the temperature roasted described in step (1)
Degree is 300~800 DEG C, and the time is 1~10 hour.
7. a kind of O composite metallic oxide catalyst, which is characterized in that including claim 1-4 any one of them modified supports
Or the modified support being prepared according to the preparation method of claim 5 or 6 and load on the carrier there is formula (I) institute
Show the metal composite oxide of general formula.
8. O composite metallic oxide catalyst according to claim 7, which is characterized in that with the gross mass of modified support
The load factor of meter, the metal composite oxide is 10%~60%, preferably 20~50%, more preferably 25~40%.
9. the preparation method of O composite metallic oxide catalyst according to claim 7 or 8, which is characterized in that including：
(1) slurries containing required metal ion are prepared；
(2) slurries described in step (1) are evaporated, are carried on the modified support surface, dry, roasting obtains the compound gold
Belong to oxide catalyst.
10. the preparation method of O composite metallic oxide catalyst according to claim 9, which is characterized in that in step (2)
The temperature of the roasting is 300~420 DEG C, and the time is 1~10 hour.
11. a kind of production acrylic acid, which is characterized in that urged using the metal composite oxide described in claim 7 or 8
O composite metallic oxide catalyst catalytic oxidation propylene aldehyde production prepared by agent or method according to claim 9 or 10
Acrylic acid.
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| CN110280257A (en) * | 2019-07-10 | 2019-09-27 | 兰州科润化工技术有限公司 | A kind of acrylic acid catalyst and preparation method thereof |
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