CN109569577A - O composite metallic oxide catalyst and its preparation method and application - Google Patents
O composite metallic oxide catalyst and its preparation method and application Download PDFInfo
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- CN109569577A CN109569577A CN201910036616.7A CN201910036616A CN109569577A CN 109569577 A CN109569577 A CN 109569577A CN 201910036616 A CN201910036616 A CN 201910036616A CN 109569577 A CN109569577 A CN 109569577A
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl 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 present invention provides a kind of O composite metallic oxide catalysts and its preparation method and application, are related to catalyst technical field.The O composite metallic oxide catalyst is Mo-V-Te-Nb-Ce-O catalyst, wherein, the doping of Ce element can provide more Lattice Oxygens for the reaction process of oxidation of propane acrylic acid in catalyst, to increase substantially the catalytic performance of catalyst, it is applied in the reaction of oxidation of propane acrylic acid, the indexs such as conversion of propane, acrylic acid selectivity, acrylic acid yield and space-time yield can be made to be in preferable level.The present invention also provides the preparation method of above-mentioned O composite metallic oxide catalyst, which can be such that Ce element is evenly distributed in O composite metallic oxide catalyst body phase, give full play to its oxygen storage capacity, to increase substantially the performance of catalyst；In addition, the preparation method process flow is simple and with good stability and repeatable, it is suitable for industrial volume production.
Description
Technical field
The present invention relates to catalyst technical fields, in particular to O composite metallic oxide catalyst and its preparation side
Method and application.
Background technique
Acrylic acid (Acrylic Acid) is a kind of organic compound, can be used as a variety of chemically treated precursors and industry
The intermediate of processing, such as surface covering, plastic additive, textile, sealant and adhesive, especially acrylics and its
Series of products are rapidly developed in recent years.With the aggravation of relieving and the aging of two tire policy of China, for diaper, defend
The potential of demand of raw towel is huge, and as the downstream product of acrylic acid, it is raw that super absorbent resin exactly makes diaper, sanitary napkin etc.
The raw material for applying flexibly product have been reported that and show that acrylic acid market scale is expected to reach 19,500,000,000 U.S. dollars in 2022, and 2016 arrive
Compound Annual Growth Rate in 2022 reaches 6.6%.
The acrylic acid preparation process of industrial mainstream is propylene two-step method at present, and propylene is first oxidized to methacrylaldehyde, propylene
Aldehyde is further oxidized to acrylic acid, and propylene is mainly derived from oil refining, increasingly exhausted with petroleum resources, propylene two-step method
Raw material sources will be very limited, and its price is higher.In contrast, propylene is prepared using the cheaper propane of price
Acid has tempting prospect.Propane is the main component of casing-head gas, natural gas, refinery gas, abundance, and price only has third
60% or so of alkene, simultaneously because propane can a step be oxidized to acrylic acid, process route is short, low energy consumption, and more friendly to environment
It is good.
The catalyst that one step of propane aoxidizes acrylic acid processed at present mainly has vanadium phosphorus oxygen (V-P-O), heteropoly acid (HPCs) and answers
Metal oxide (MMO) the three classes system of conjunction.Wherein V-P-O has been successfully applied to the industrial production of butane oxidation production of maleic anhydride
In, but for selective oxidation of propane acrylic acid, the effect is unsatisfactory, and one-way yield is often no more than 13%；Heteropolyacid system
Have the advantages that structure-controllable, but be easy to inactivate because of structure collapses under the operation temperature higher than 400 DEG C, thermal stability compared with
Difference.Since nineteen ninety, extensive research has been obtained by the O composite metallic oxide catalyst system of representative of MoV base catalyst.
Although O composite metallic oxide catalyst aoxidizes in acrylic acid reaction processed in propane selectivity and achieves certain catalytic effect,
It is that its whole catalytic performance need further to be promoted.
In view of this, the present invention is specifically proposed at least one of to solve the above technical problems.
Summary of the invention
The first purpose of this invention is to provide a kind of O composite metallic oxide catalyst, which urges
Agent is Mo-V-Te-Nb-Ce-O catalyst, has good catalytic performance, can be applied to the reaction of oxidation of propane acrylic acid
In the process.
Second object of the present invention is to provide a kind of preparation method of O composite metallic oxide catalyst, and Ce can be made first
Element is evenly distributed in O composite metallic oxide catalyst body phase, and obtained Mo-V-Te-Nb-Ce-O catalyst has good
Catalytic performance, and the preparation method process flow is simple, with good stability and repeatable, is suitable for industrializing
Volume production.
Third object of the present invention is that providing above-mentioned O composite metallic oxide catalyst or metal composite oxide urges
The application of the preparation method of agent.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention provides a kind of O composite metallic oxide catalyst, the O composite metallic oxide catalyst is Mo-V-
Te-Nb-Ce-O catalyst；
Wherein, the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce are 1:(0.22-0.32): (0.12-0.25):
(0.11-0.15): (0.0025-0.015).
Further, on the basis of technical solution of the present invention, in the Mo-V-Te-Nb-Ce-O catalyst, Mo, V,
The relative mole ratios of five kinds of elements of Te, Nb and Ce are 1:(0.25-0.3): (0.18-0.23): (0.12-0.14): (0.003-
0.01)。
Further, on the basis of technical solution of the present invention, the preparation side of the O composite metallic oxide catalyst
Method, comprising the following steps:
The mixed solution that the source Mo, the source V, the source Te, the source Ce and organic acid are mixed to form is provided；
Mixed solution is mixed with the source Nb, is reacted, the mixed serum that reaction obtains is dried and is roasted, is obtained compound
Metal oxide catalyst.
Further, on the basis of technical solution of the present invention, the source Ce includes cerous nitrate and/or ammonium ceric nitrate,
Preferably ammonium ceric nitrate.
Further, on the basis of technical solution of the present invention, the organic acid accounts for the quality point of Mo element in the source Mo
Number is 2-15wt%, preferably 5-10wt%.
And/or the organic acid include in citric acid, oxalic acid or ascorbic acid any one or at least two group
It closes, preferably citric acid.
Further, on the basis of technical solution of the present invention, Mo, V, Te, Ce and Nb metal in the mixed serum
The total mol concentration of ion is 0.1-0.6mol/L, preferably 0.2-0.4mol/L.
Further, on the basis of technical solution of the present invention, the preparation side of the O composite metallic oxide catalyst
Method, comprising the following steps:
Solution containing organic acid is provided, the source Mo, the source V and the source Te is added in the solution of Xiang Hanyou organic acid, then adds again
Enter the source Ce, obtains the mixed solution that the source Mo, the source V, the source Te, the source Ce and organic acid are mixed to form；
Solution containing the source Nb is provided, the solution containing the source Nb is added into mixed solution, reaction obtains mixed serum；
It is aged after adjusting the pH to 1.0-4.0 of mixed serum, dry, roasting obtains O composite metallic oxide catalyst.
Further, it on the basis of technical solution of the present invention, is added and is contained into mixed solution by the way of dropwise addition
There are the solution in the source Nb, drop rate 2-10mL/min, preferably 4-8mL/min；
And/or digestion time 1-4h；
And/or the drying is revolving drying or spray drying.
Further, on the basis of technical solution of the present invention, the roasting includes primary roasting and after baking；
The maturing temperature once roasted is 280-380 DEG C, calcining time 2-6h, and calcination atmosphere is oxygen or sky
Gas；
The maturing temperature of the after baking is 580-600 DEG C, calcining time 2-8h, and calcination atmosphere is protectiveness gas
Atmosphere.
The present invention also provides above-mentioned O composite metallic oxide catalyst or use above-mentioned O composite metallic oxide catalyst
Preparation method made from O composite metallic oxide catalyst propane prepare acrylic acid reaction in application.
Compared with prior art, O composite metallic oxide catalyst provided by the invention and its preparation method and application has
Following advantage:
(1) the present invention provides a kind of O composite metallic oxide catalyst, which is Mo-V-
Te-Nb-Ce-O catalyst, wherein the doping of Ce element can provide in catalyst for the reaction process of oxidation of propane acrylic acid
More Lattice Oxygens are applied to the reaction of oxidation of propane acrylic acid to increase substantially the catalytic performance of catalyst
In, so that the indexs such as conversion of propane, acrylic acid selectivity, acrylic acid yield and space-time yield are in preferable level.
(2) the present invention provides a kind of preparation methods of O composite metallic oxide catalyst, first by the source Ce and the source Mo, V
Source, the source Te form uniform and clear mixed solution under the complexing of organic acid, and Nb is then added into mixed solution again
Source carries out reaction and generates precipitating, then using a series of dryings, roasting, obtains O composite metallic oxide catalyst, the preparation
Method can be such that Ce element is evenly distributed in O composite metallic oxide catalyst body phase, give full play to its oxygen storage capacity, thus greatly
The performance of amplitude raising catalyst；
In addition, the preparation method process flow is simple and with good stability and repeatable, it is suitable for industry
Change volume production.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
It should be understood that in the present invention, if without particularly illustrating, all embodiments mentioned in this article and
Preferred implementation method can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating
Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating
The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a~b " indicates the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as numberical range " 6~22 " indicate herein all listed " 6~22 " it
Between whole real numbers, " 6~22 " be these combinations of values breviary indicate.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, it is each reaction or operating procedure can sequentially carry out, can also in sequence into
Row.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
According to an aspect of the invention, there is provided O composite metallic oxide catalyst, the composite metal oxide catalyst
Agent is Mo-V-Te-Nb-Ce-O catalyst；
Wherein, the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce are 1:(0.22-0.32): (0.12-0.25):
(0.11-0.15): (0.0025-0.015).
Mo-V-Te-Nb-Ce-O catalyst is mainly the composite metal oxide catalyst being made of Mo, V, Te, Nb, Ce, O
Agent.
In the reaction of oxidation of propane acrylic acid, participating in reaction is the Lattice Oxygen in catalyst, and Ce element has
Ce element doping is formed Mo-V-Te-Nb-Ce-O catalyst into Mo-V-Te-Nb-O by good oxygen storage capacity, can be reaction
Process provides more Lattice Oxygens, to increase substantially the catalytic performance of catalyst.
Have for the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce in Mo-V-Te-Nb-Ce-O catalyst certain
It limits, so that the Mo-V-Te-Nb-Ce-O catalyst has good catalytic performance.
As a kind of optional embodiment of the present invention, in Mo-V-Te-Nb-Ce-O catalyst, five kinds of Mo, V, Te, Nb and Ce
The relative mole ratios of element are 1:(0.25-0.3): (0.18-0.23): (0.12-0.14): (0.003-0.01).
Five kinds of typical but non-limiting relative mole ratios of element of Mo, V, Te, Nb and Ce are 1:0.22:0.17:0.14:
0.0025、1:0.25:0.17:0.14:0.0025、1:0.28:0.17:0.14:0.0025、1:0.3:0.23:0.12:0.005、
1:0.22:0.2:0.15:0.0025、1:0.25:0.13:0.12:0.0025、1:0.25:0.23:0.13:0.0025、1:
0.25:0.23:0.15:0.003、1:0.25:0.23:0.15:0.005、1:0.25:0.23:0.15:0.0075、1:0.25:
0.23:0.15:0.009,1:0.25:0.23:0.14:0.010 or 1:0.3:0.23:0.15:0.015.
According to the second aspect of the invention, the preparation method of above-mentioned O composite metallic oxide catalyst is additionally provided, is wrapped
Include following steps:
The mixed solution that the source Mo, the source V, the source Te, the source Ce and organic acid are mixed to form is provided；
Mixed solution is mixed with the source Nb, is reacted, the mixed serum that reaction obtains is dried, roasts, obtains compound
Metal oxide catalyst.
The source Mo, the source V, the source Te, the source Ce and the source Nb can be used molybdenum salt commonly used in the art, vanadic salts, tellurium compound, cerium salt and
Niobium salt is not especially limited selected substance classes, can be selected according to real reaction system.
Organic acid primarily serves complexing, is to carry out complex reaction between the source Mo, the source V, the source Te and the source Ce, mainly
Generate complexing with the source Mo, at the same enable the source Ce uniform be dispersed in the source Mo, in the solution that the source V and the source Te are formed, to make
The mixed solution that the source Mo, the source V, the source Te, the source Ce and organic acid are formed more is clarified.If being not added with organic acid, only by the source Ce
It is added in the clear solution that the source Mo, the source V and the source Te are formed, then solution can become muddy after the source Ce is added, and illustrate adding for the source Ce
Enter so that there is insoluble matter generation in solution, GuCeYuan cannot disperse well in the solution.Therefore whether organic acid adds direct pass
It is that whether can be uniformly dispersed in solution existing for the source Mo, the source V and the source Te to the source Ce.
In addition, organic acid has certain reduction to the source Mo, blue molybdenum can be formed, is conducive to the formation of active phase, makes to be made
O composite metallic oxide catalyst have very high catalytic activity and selectivity.
The specific type of organic acid is not construed as limiting, as long as complexing can occur between the source Mo, the source V, the source Te and the source Ce
?.
In the present invention, the source Ce is formed under the complexing of organic acid with the source Mo, the source V, the source Te first uniform and clear
Clear mixed solution, then again into mixed solution be added the source Nb carry out reaction generate precipitating, then using a series of dryings,
Roasting, obtains O composite metallic oxide catalyst, which can make Ce element be evenly distributed on metal composite oxide to urge
In agent body phase, its oxygen storage capacity is given full play to, to increase substantially catalyst performance.
In addition, the preparation method process flow is simple and with good stability and repeatable, it is suitable for industry
Change volume production.
The source Mo, the source V, the source Te, the source Ce and the source Nb generally use compound salt commonly used in the art.
As a kind of optional embodiment of the present invention, the source Mo includes appointing in ammonium dimolybdate, ammonium tetramolybdate or ammonium paramolybdate
It anticipates a kind of or at least two combinations；
As a kind of optional embodiment of the present invention, the source V includes vanadic sulfate and/or ammonium metavanadate；
As a kind of optional embodiment of the present invention, the source Te includes in tellurium dioxide, sodium tellurite, telluric acid or llurate
Any one or at least two combination；
As a kind of optional embodiment of the present invention, the source Ce includes cerous nitrate and/or ammonium ceric nitrate, preferably cerous nitrate
Ammonium.
As a kind of optional embodiment of the present invention, the source Nb includes niobium oxalate and/or ammonium niobium oxalate.
By to the source Mo, the source V, the source Te, the specific kind of restriction in the source Ce and the source Nb, so that having between each raw material good
Matching relationship, so that the performance for the Mo-V-Te-Nb-Ce-O catalyst being prepared be made to be in preferably horizontal.
Also there is certain requirement for the dosage of organic acid, the dosage of organic acid is very few, then the source Ce and the source Mo, the source V, the source Te
It is hardly formed clear solution, if dosage is excessive, organic acid can be by the source Mo over reduction, so that it is anti-to influence subsequent co-precipitation
It answers.Therefore the dosage of organic acid should control within the appropriate range.
As a kind of optional embodiment of the present invention, the mass fraction that organic acid accounts for Mo element in the source Mo is 2-15%, excellent
Select 5-10%.
It should be noted that the quality of Mo element is by Mo simple substance when Mo ion is scaled Mo simple substance in the source Mo in the source Mo
Quality.Typical but non-limiting organic acid account for Mo element in the source Mo mass fraction be 2%, 4%, 5%, 6%, 8%,
10%, 12%, 14% or 15%.
The specific type of organic acid also influences whether dispersity of the source Ce in entire mixed solution.
As a kind of optional embodiment of the present invention, organic acid includes any one in citric acid, oxalic acid or ascorbic acid
Kind or at least two combination, preferably citric acid.
The organic acids such as citric acid, oxalic acid or ascorbic acid can be complexed with the source Mo, form uniform clarification after the source Ce is added
Solution, and itself has week reduction, and Mo can be carried out to appropriateness reduction and form blue molybdenum, be conducive to active phase in roasting process
It generates.In addition, citric acid, oxalic acid or ascorbic acid can decompose in roasting process, increase specific surface area of catalyst, improves catalysis
Agent pore structure.
After the mixed solution that the source Mo, the source V, the source Te, the source Ce and organic acid are mixed to form is mixed with the source Nb, it can occur coprecipitated
It forms sediment and reacts, generate Chinese red precipitating, obtain mixed serum (being referred to as body liquid before catalyst).
As a kind of optional embodiment of the present invention, the total moles of Mo, V, Te, Ce and Nb metal ion are dense in mixed serum
Degree is 0.1-0.6mol/L, preferably 0.2-0.4mol/L；The total mol concentration of typical but infinite metal ion is 0.1mol/
L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L or 0.6mol/L.
By the restriction to metal ion total mol concentration in mixed serum, so that the O composite metallic oxide catalyst
Performance and preparation efficiency are in preferable level.
As a kind of optional embodiment of the present invention, the preparation method of O composite metallic oxide catalyst, including following step
It is rapid:
Solution containing organic acid is provided, the source Mo, the source V and the source Te is added in the solution of Xiang Hanyou organic acid, then adds again
Enter the source Ce, obtains the mixed solution that the source Mo, the source V, the source Te, the source Ce and organic acid are mixed to form；
Solution containing the source Nb is provided, the solution containing the source Nb is added into mixed solution, reaction obtains mixed serum；
It is aged after adjusting the pH value to 1.0-4.0 of mixed serum, dry, roasting obtains O composite metallic oxide catalyst.
Acid solution can be used the pH value of mixed serum is adjusted.Preferably, acid solution is nitric acid solution, nitric acid solution
Concentration is 10-20wt%, typical but non-limiting nitric acid solution concentration be 10wt%, 12wt%, 14wt%, 15wt%,
16wt%, 18wt% or 20wt%.
The pH value of mixed serum is 1.0-4.0, preferably 1.5-2.8 after adjusting.By adjusting the pH value of mixed serum, make
It obtains and is sufficiently reacted between each metal ion species, the presoma formed under the conditions of pH appropriate is conducive to activate third in roasting
The formation of the crystal phase structure of alkane.
By to the charging sequence in the source Ce, the adjusting of mixed serum pH and ageing in above-mentioned preparation method and etc. limit
It is fixed, so that the performance of preparation-obtained O composite metallic oxide catalyst is more preferable.
As a kind of optional embodiment of the present invention, it is added by the way of dropwise addition into mixed solution and contains the molten of the source Nb
Liquid, drop rate 2-10mL/min, preferably 4-8mL/min；Typical but non-limiting drop rate be 2mL/min,
4mL/min, 5mL/min, 6mL/min, 8mL/min or 10mL/min.Pass through the limit of the drop rate to the solution containing the source Nb
It is fixed, so that coprecipitation reaction carries out more abundant.
As a kind of optional embodiment of the present invention, digestion time 1-4h；Typical but non-limiting digestion time is
1h, 2h, 3h or 4h.Ageing may make the further crystallization of the presoma to be formed, and form the uniform crystal grain of granule size.
It after mixed serum is aged, then is dried to remove moisture therein, obtains catalyst precursor.As this hair
A kind of bright optional embodiment, it is dry for revolving drying or spray drying.By the restriction of specific drying mode, so that giving birth to
At catalyst precursor grain diameter it is more uniform, disperse it is also more uniform.
Preferably, dry for spray drying.Outlet temperature is not less than 80 DEG C when spray drying.
Product (catalyst precursor) after drying is roasted, to obtain O composite metallic oxide catalyst.Roasting
The influence O composite metallic oxide catalyst that maturing temperature, calcining time and calcination atmosphere can be different degrees of during burning
Catalytic activity.
As a kind of optional embodiment of the present invention, roasting includes primary roasting and after baking；
The maturing temperature once roasted is 280-380 DEG C, calcining time 2-6h, and calcination atmosphere is oxygen or air；Allusion quotation
Type but unrestricted maturing temperature are 280 DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C, 350 DEG C, 360
DEG C, 370 DEG C or 380 DEG C, typical but non-limiting calcining time be 2h, 3h, 4h, 5h or 6h.
The maturing temperature of after baking is 580-600 DEG C, and calcining time 2-8h, calcination atmosphere is protective atmosphere；Allusion quotation
Type but unrestricted maturing temperature are 580 DEG C, 585 DEG C, 590 DEG C, 595 DEG C or 600 DEG C, when typical but non-limiting roasting
Between be 2h, 3h, 4h, 5h, 6h, 7h or 8h, calcination atmosphere can be for nitrogen or argon gas etc..
It should be noted that after primary roasting then Temperature fall carries out after baking to room temperature again.Once roast
Heating rate is 1-5 DEG C/min, and preferably 3 DEG C/min, the heating rate of after baking is 1-3 DEG C/min, preferably 2 DEG C/min.
The catalyst powder obtained after roasting is subjected to compression molding, is crushed after making certain mesh number to get to can be used for third
The O composite metallic oxide catalyst of alkane Selective Oxidation acrylic acid reaction.
According to the third aspect of the present invention, above-mentioned O composite metallic oxide catalyst is additionally provided or using above-mentioned compound
Reaction of the O composite metallic oxide catalyst made from the preparation method of metal oxide catalyst in oxidation of propane acrylic acid
In application.
In view of above-mentioned O composite metallic oxide catalyst or using the preparation method of above-mentioned O composite metallic oxide catalyst
Advantage possessed by O composite metallic oxide catalyst obtained is applied in the reaction of oxidation of propane acrylic acid, can
The index parameters such as conversion of propane, acrylic acid selectivity, acrylic acid yield and space-time yield are significantly improved, are industrial propane oxygen
Change acrylic acid processed and provides more foundations.
Combined with specific embodiments below and comparative example, the invention will be further described.
Embodiment 1
A kind of O composite metallic oxide catalyst is present embodiments provided, the O composite metallic oxide catalyst is Mo-
V-Te-Nb-Ce-O catalyst；
Wherein, the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce are 1:0.3:0.23:0.12:0.005.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, comprising the following steps:
(a) organic acid is added into 80 DEG C of deionized waters, is separately added into stoichiometry in the solution of Xiang Hanyou organic acid
Then the source Mo, the source V and the source Te, heating stirring 1h add the source Ce, the reaction was continued 3h, obtain the source Mo, the source V, the source Te, the source Ce and
The mixed solution that organic acid is mixed to form；
Wherein, organic acid is citric acid, and citric acid quality accounts for 10% of Mo element quality in the source Mo；The source Mo is para-molybdic acid
Ammonium, the source V are ammonium metavanadate, and the source Te is telluric acid, and the source Ce is ammonium ceric nitrate；
(b) solution containing the source Nb is added drop-wise in above-mentioned mixed solution, is reacted, generated salmon precipitation, mixed
Slurries；Wherein, the total mol concentration of Mo, V, Te, Ce and Nb metal ion is 0.2-0.3mol/L in mixed serum；
(c) it uses concentration to adjust the pH to 2.8-3.0 of mixed serum for the nitric acid solution of 15wt%, is then aged 2h, spray
Mist is dry, and spray dryer outlet temperature is not less than 85 DEG C, is then successively once roasted in air atmosphere and in nitrogen
After baking is carried out under gas atmosphere, obtains product of roasting；Wherein, maturing temperature is 350 DEG C, calcining time 3h, secondary
Maturing temperature is 590 DEG C, calcining time 2h；
By product of roasting compression molding, it is crushed to 20-40 mesh, obtains O composite metallic oxide catalyst.
Embodiment 2
A kind of O composite metallic oxide catalyst is present embodiments provided, the O composite metallic oxide catalyst is Mo-
V-Te-Nb-Ce-O catalyst；
Wherein, the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce are 1:0.25:0.23:0.13:0.0025.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition in step (b) in mixed serum
The total mol concentration of Mo, V, Te, Ce and Nb metal ion is 0.5mol/L, remaining step and parameter are same as Example 1.
Embodiment 3
Present embodiments provide a kind of O composite metallic oxide catalyst, specific group of the O composite metallic oxide catalyst
At same as Example 1.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition to organic acid uses oxalic acid, remaining
Step is same as Example 1 with parameter.
Embodiment 4
Present embodiments provide a kind of O composite metallic oxide catalyst, specific group of the O composite metallic oxide catalyst
At same as Example 1.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition to organic acid uses ascorbic acid,
Remaining step and parameter are same as Example 1.
Embodiment 5
Present embodiments provide a kind of O composite metallic oxide catalyst, specific group of the O composite metallic oxide catalyst
At same as Example 1.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition to organic acid uses organic acid for lemon
Lemon acid, citric acid quality account for 6% of Mo element quality in the source Mo, remaining step and parameter are same as Example 1.
Embodiment 6
Present embodiments provide a kind of O composite metallic oxide catalyst, specific group of the O composite metallic oxide catalyst
At same as Example 1.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition to organic acid uses organic acid for lemon
Lemon acid, citric acid quality account for 1% of Mo element quality in the source Mo, remaining step and parameter are same as Example 1.
Embodiment 7
Present embodiments provide a kind of O composite metallic oxide catalyst, specific group of the O composite metallic oxide catalyst
At same as Example 1.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition to organic acid uses organic acid for lemon
Lemon acid, citric acid quality account for 17% of Mo element quality in the source Mo, remaining step and parameter are same as Example 1.
Embodiment 8
Present embodiments provide a kind of O composite metallic oxide catalyst, specific group of the O composite metallic oxide catalyst
At same as Example 1.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition to the source Ce is cerous nitrate, remaining step
Suddenly same as Example 1 with parameter.
Embodiment 9
Present embodiments provide a kind of O composite metallic oxide catalyst, specific group of the O composite metallic oxide catalyst
At same as Example 1.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition to being steamed in step (c) using rotation
Hair replaces spray drying, the temperature 45 C of rotary evaporation, revolving speed 50r/min, vacuum degree -0.09MPa, remaining step and parameter with
Embodiment 1 is identical.
Embodiment 10
A kind of O composite metallic oxide catalyst is present embodiments provided, the O composite metallic oxide catalyst is Mo-
V-Te-Nb-Ce-O catalyst；
Wherein, the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce are 1:0.25:0.13:0.12:0.01.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, comprising the following steps:
(a) organic acid is added into 80 DEG C of deionized waters, is separately added into stoichiometry in the solution of Xiang Hanyou organic acid
Then the source Mo, the source V and the source Te, heating stirring 1h add the source Ce, the reaction was continued 3h, obtain the source Mo, the source V, the source Te, the source Ce and
The mixed solution that organic acid is mixed to form；
Wherein, organic acid is citric acid, and citric acid quality accounts for 2% of Mo element quality in the source Mo；The source Mo is ammonium molybdate, V
Source is vanadic sulfate, and the source Te is llurate, and the source Ce is ammonium ceric nitrate；
(b) solution containing the source Nb is added drop-wise in above-mentioned mixed solution, is reacted, generated salmon precipitation, mixed
Slurries；Wherein, the total mol concentration of Mo, V, Te, Ce and Nb metal ion is 0.1mol/L in mixed serum；
(c) it uses concentration to adjust the pH to 3.5-4.0 of mixed serum for the nitric acid solution of 10wt%, is then aged 3h, spray
Mist is dry, and spray dryer outlet temperature is not less than 85 DEG C, is then successively once roasted in air atmosphere and in nitrogen
After baking is carried out under gas atmosphere, obtains product of roasting；Wherein, maturing temperature is 300 DEG C, calcining time 4h, secondary
Maturing temperature is 600 DEG C, calcining time 3h；
By product of roasting compression molding, it is crushed to 20-40 mesh, obtains O composite metallic oxide catalyst.
Embodiment 11
Present embodiments provide a kind of O composite metallic oxide catalyst, specific group of the O composite metallic oxide catalyst
At same as in Example 10.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, in addition to organic acid uses organic acid for lemon
Lemon acid, citric acid quality account for 5% of Mo element quality in the source Mo, remaining step and parameter are same as in Example 10.
Embodiment 12
A kind of O composite metallic oxide catalyst is present embodiments provided, the O composite metallic oxide catalyst is Mo-
V-Te-Nb-Ce-O catalyst；
Wherein, the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce are 1:0.26:0.18:0.13:0.005.
The preparation method of O composite metallic oxide catalyst provided in this embodiment, comprising the following steps:
(a) organic acid is added into 80 DEG C of deionized waters, is separately added into stoichiometry in the solution of Xiang Hanyou organic acid
Then the source Mo, the source V and the source Te, heating stirring 1h add the source Ce, the reaction was continued 3h, obtain the source Mo, the source V, the source Te, the source Ce and
The mixed solution that organic acid is mixed to form；
Wherein, organic acid is citric acid and ascorbic acid (mass ratio 2:1), and the gross mass of citric acid and ascorbic acid accounts for Mo
The 10% of Mo element quality in source；The source Mo is ammonium molybdate, and the source V is vanadic sulfate, and the source Te is llurate, and the source Ce is ammonium ceric nitrate；
(b) solution containing the source Nb is added drop-wise in above-mentioned mixed solution, is reacted, generated salmon precipitation, mixed
Slurries；Wherein, the total mol concentration of Mo, V, Te, Ce and Nb metal ion is 0.6mol/L in mixed serum；
(c) it uses concentration to adjust the pH to 1.0-1.5 of mixed serum for the nitric acid solution of 20wt%, is then aged 4h, spray
Mist is dry, and spray dryer outlet temperature is not less than 85 DEG C, is then successively once roasted in air atmosphere and in nitrogen
After baking is carried out under gas atmosphere, obtains product of roasting；Wherein, maturing temperature is 380 DEG C, calcining time 2h, secondary
Maturing temperature is 580 DEG C, calcining time 7h；
By product of roasting compression molding, it is crushed to 20-40 mesh, obtains O composite metallic oxide catalyst.
Embodiment 13
This comparative example provides a kind of O composite metallic oxide catalyst, the composition of the O composite metallic oxide catalyst with
Embodiment 11 is identical.
The preparation method for the O composite metallic oxide catalyst that this comparative example provides, in addition to organic acid is adopted in step (a)
With tartaric acid, remaining step and parameter are same as Example 1.
Comparative example 1
This comparative example provides a kind of O composite metallic oxide catalyst, the composition of the O composite metallic oxide catalyst with
Embodiment 1 is identical.
The preparation method for the O composite metallic oxide catalyst that this comparative example provides, comprising the following steps:
(a) organic acid is added into 80 DEG C of deionized waters, is separately added into stoichiometry in the solution of Xiang Hanyou organic acid
The source Mo, the source V and the source Te, heating stirring 3h obtain the mixed solution that the source Mo, the source V, the source Te and organic acid are mixed to form；
Wherein, organic acid is citric acid, and citric acid quality accounts for 10% of Mo element quality in the source Mo；The source Mo is para-molybdic acid
Ammonium, the source V are ammonium metavanadate, and the source Te is telluric acid；
(b) solution containing the source Nb is added drop-wise in above-mentioned mixed solution, is reacted, generate salmon precipitation, then added again
Enter the solution containing the source Ce, obtains mixed serum；Wherein, the source Ce is ammonium ceric nitrate, Mo, V, Te, Ce and Nb gold in mixed serum
The total mol concentration for belonging to ion is 0.2-0.3mol/L；
The step of step (c), is same as Example 1 with parameter.
Comparative example 2
This comparative example provides a kind of O composite metallic oxide catalyst, the composition of the O composite metallic oxide catalyst with
Embodiment 1 is identical.
The preparation method for the O composite metallic oxide catalyst that this comparative example provides, comprising the following steps:
(a) organic acid is added into 80 DEG C of deionized waters, is separately added into stoichiometry in the solution of Xiang Hanyou organic acid
The source Mo, the source V and the source Te, heating stirring 3h obtain the mixed solution that the source Mo, the source V, the source Te and organic acid are mixed to form；
Wherein, organic acid is citric acid, and citric acid quality accounts for 10% of Mo element quality in the source Mo；The source Mo is para-molybdic acid
Ammonium, the source V are ammonium metavanadate, and the source Te is telluric acid；
(b) solution containing the source Nb and the solution containing the source Ce are added drop-wise in above-mentioned mixed solution simultaneously, are reacted, it is raw
At precipitating, mixed serum is obtained；Wherein, the source Ce is ammonium ceric nitrate, and Mo, V, Te, Ce and Nb metal ion is total in mixed serum
Molar concentration is 0.2-0.3mol/L；
The step of step (c), is same as Example 1 with parameter.
Comparative example 3
This comparative example provides a kind of O composite metallic oxide catalyst, the composition of the O composite metallic oxide catalyst with
Embodiment 1 is identical.
The preparation method for the O composite metallic oxide catalyst that this comparative example provides, comprising the following steps:
(a) it is separately added into the source Mo, the source V, the source Te and the source Ce of stoichiometry into 80 DEG C of deionized waters, has at this time obvious muddy
Turbid generation, is unable to get clear solution, and heating stirring 3h obtains the mixed solution that the source Mo, the source V, the source Te and the source Ce are mixed to form；
Wherein, the source Mo is ammonium paramolybdate, and the source V is ammonium metavanadate, and the source Te is telluric acid, and the source Ce is ammonium ceric nitrate；
Step (b) and step (c) are same as Example 1.
Comparative example 4
This comparative example provides a kind of O composite metallic oxide catalyst, and the group of the O composite metallic oxide catalyst becomes
Mo-V-Te-Nb-O catalyst；
Wherein, the relative mole ratios of tetra- kinds of elements of Mo, V, Te and Nb are 1:0.3:0.23:0.12.
This comparative example provide O composite metallic oxide catalyst preparation method, in addition to be not added in step (b) containing
The solution in the source Ce, remaining step are identical as comparative example 1.
Comparative example 5
This comparative example provides a kind of O composite metallic oxide catalyst, and the group of the O composite metallic oxide catalyst becomes
Mo-V-Te-Nb-O catalyst；
Wherein, the relative mole ratios of tetra- kinds of elements of Mo, V, Te and Nb are 1:0.3:0.23:0.12.
The preparation method for the O composite metallic oxide catalyst that this comparative example provides, it is organic in addition to not being added in step (a)
Acid is not added with the solution containing the source Ce in step (b), remaining step is identical as comparative example 1.
For the effect for verifying embodiment and comparative example, ad hoc following experimental example.
Experimental example 1
The embodiment 1-13 and comparative example 1-5 O composite metallic oxide catalyst prepared is used for oxidation of propane acrylic acid
Reaction.2.8g O composite metallic oxide catalyst is weighed respectively, and unstrpped gas forms V (C3H8):V(O2):V(H2O):V(N2)=
1:2:5:9,380 DEG C of reaction temperature, propane air speed is 300h-1, reaction time 20h, conversion of propane, acrylic acid selectivity,
Acrylic acid yield, space-time yield are as shown in table 1:
Table 1
It can be seen from the data in Table 1 that the catalytic performance for the O composite metallic oxide catalyst that embodiment provides is on the whole
The catalytic performance of the O composite metallic oxide catalyst of comparative example offer is provided.
Specifically, it can be seen from the data in Table 1 that the addition in the source Ce significantly improves O composite metallic oxide catalyst
Activity and selectivity.But the addition manner in the source Ce is most important, the source Mo, the source V, the source Te and the source Nb formed co-precipitation after be added or
It is added together with the source Nb in the source Mo, the source V and the source Te solution and forms co-precipitation, do not have the effect for improving catalyst performance.?
So that the effect of organic acid is extremely important, organic being not added during the source Ce evenly spreads to the source Mo, the source V and the source Te solution
Under conditions of acid, uniform, clear solution can not be formed, and the type of organic acid and the amount of addition urge metal composite oxide
Agent performance also has a significant impact, and exceeds its use scope, catalyst performance can be made to decline instead.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of O composite metallic oxide catalyst, which is characterized in that the O composite metallic oxide catalyst is Mo-V-Te-
Nb-Ce-O catalyst；
Wherein, the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce are 1:(0.22-0.32): (0.12-0.25): (0.11-
0.15): (0.0025-0.015).
2. O composite metallic oxide catalyst according to claim 1, which is characterized in that the Mo-V-Te-Nb-Ce-O
In catalyst, the relative mole ratios of five kinds of elements of Mo, V, Te, Nb and Ce are 1:(0.25-0.3): (0.18-0.23): (0.12-
0.14): (0.003-0.01).
3. the preparation method of O composite metallic oxide catalyst of any of claims 1 or 2, which is characterized in that including following step
It is rapid:
The mixed solution that the source Mo, the source V, the source Te, the source Ce and organic acid are mixed to form is provided；
Mixed solution is mixed with the source Nb, is reacted, the mixed serum that reaction obtains is dried and is roasted, composition metal is obtained
Oxide catalyst.
4. the preparation method of O composite metallic oxide catalyst according to claim 3, which is characterized in that the source the Ce packet
Include cerous nitrate and/or ammonium ceric nitrate, preferably ammonium ceric nitrate.
5. the preparation method of O composite metallic oxide catalyst according to claim 3, which is characterized in that the organic acid
The mass fraction for accounting for Mo element in the source Mo is 2-15wt%, preferably 5-10wt%；
And/or the organic acid include in citric acid, oxalic acid or ascorbic acid any one or at least two combination, it is excellent
It is selected as citric acid.
6. the preparation method of O composite metallic oxide catalyst according to claim 3, which is characterized in that the mixing slurry
The total mol concentration of Mo, V, Te, Ce and Nb metal ion is 0.1-0.6mol/L, preferably 0.2-0.4mol/L in liquid.
7. according to the preparation method of O composite metallic oxide catalyst described in claim 3-6 any one, which is characterized in that
The following steps are included:
Solution containing organic acid is provided, the source Mo, the source V and the source Te is added in the solution of Xiang Hanyou organic acid, then adds Ce
Source obtains the mixed solution that the source Mo, the source V, the source Te, the source Ce and organic acid are mixed to form；
Solution containing the source Nb is provided, the solution containing the source Nb is added into mixed solution, reaction obtains mixed serum；
It is aged after adjusting the pH to 1.0-4.0 of mixed serum, dry, roasting obtains O composite metallic oxide catalyst.
8. the preparation method of O composite metallic oxide catalyst according to claim 7, which is characterized in that using what is be added dropwise
The solution containing the source Nb, drop rate 2-10mL/min, preferably 4-8mL/min are added into mixed solution for mode；
And/or digestion time 1-4h；
And/or the drying is revolving drying or spray drying.
9. according to the preparation method of O composite metallic oxide catalyst described in claim 3-6 any one, which is characterized in that
The roasting includes primary roasting and after baking；
The maturing temperature once roasted is 280-380 DEG C, calcining time 2-6h, and calcination atmosphere is oxygen or air；
The maturing temperature of the after baking is 580-600 DEG C, and calcining time 2-8h, calcination atmosphere is protective atmosphere.
10. O composite metallic oxide catalyst of any of claims 1 or 2 uses described in claim 3-9 any one
O composite metallic oxide catalyst made from the preparation method of O composite metallic oxide catalyst prepares acrylic acid reaction in propane
In application.
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