CN101005892B - Catalyst composed of complex oxide - Google Patents
Catalyst composed of complex oxide Download PDFInfo
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- CN101005892B CN101005892B CN2005800278209A CN200580027820A CN101005892B CN 101005892 B CN101005892 B CN 101005892B CN 2005800278209 A CN2005800278209 A CN 2005800278209A CN 200580027820 A CN200580027820 A CN 200580027820A CN 101005892 B CN101005892 B CN 101005892B
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Abstract
Disclosed is a complex oxide catalyst composed of catalyst particles containing Mo, V, a component X and a silica-containing carrier. The component X is at least one element selected from alkaline earth metal elements and rare earth elements. The complex oxide catalyst is supported by the carrier, and the component X is uniformly distributed in the catalyst particles.
Description
Technical field
The present invention relates to be used for the catalytic gas phase oxidation of propane or iso-butane or the composite oxide catalysts of gas phase catalysis ammoxidation reaction, and by using described composite oxide catalysts to produce the method for unsaturated acids or unsaturated nitrile.
Background technology
Up to now, produce the method for corresponding unsaturated carboxylic acid or unsaturated nitrile and be widely known by the people by propylene or isobutene being carried out catalytic gas phase oxidation or gas phase catalysis ammoxidation.Yet, in recent years by using propane or iso-butane to replace propylene or isobutene, and they are carried out catalytic gas phase oxidation or gas phase catalysis ammoxidation reaction, thereby the method for producing corresponding unsaturated carboxylic acid or unsaturated nitrile attracts much attention, and has proposed various types of oxide catalysts.For example, disclosed the oxide catalyst that contains Mo-V-Nb-(Sb/Te) in the patent documentation 1 and 2.
In addition, disclosed some examples in patent documentation 1 and the patent documentation 3 to 6, wherein further improved catalyst performance by in the catalyst that contains Mo and V, adding rare earth element etc.
Promptly, when by propane or iso-butane are carried out catalytic gas phase oxidation or gas phase catalysis ammoxidation, thereby when producing corresponding unsaturated carboxylic acid or unsaturated nitrile, the catalyst that has added rare earth element etc. in containing the oxide catalyst of Mo-V is effective, as mentioned above, up to the present this catalyst has been carried out broad research.
When will the adding disclosed in patent documentation 1,3,5 and 6 having the oxide catalyst that contains Mo-V of compositions such as rare earth element to be used for the catalytic gas phase oxidation of propane or iso-butane or gas phase catalysis ammoxidation reaction, the yield of object is still unsatisfactory.Particularly, the supported catalyst that is applicable to fluidized-bed reaction has the tendency that reduces the object yield.As for the reason of reactivity worth deficiency, disclosed as patent documentation 6, known is can disadvantageous interaction take place with other metal ingredient such as adding ingredients such as rare earth elements in the operation of preparation slurry.
For example, disclose following content in the patent documentation 1,3,5 and 6: when use had the water insoluble solid of big average grain diameter, the disadvantageous interaction that is produced in the pulp preparation operation reduced, thereby had improved the yield of object.Yet, in above-mentioned patent documentation,, and, when the manufacture catalyst, also have the risk of blocking pipeline because the solid material in using is water insoluble not only without any about adding the uniformly dispersed description of element in catalyst component.In addition, when adding excessive rare earth element etc., the oxide particle of being made by adding ingredient can be exposed on the surface of catalyst, and this will promote the decomposition reaction of object, thereby reduce yield.
Disclose a kind of infusion process in the patent documentation 4, wherein required element has been added through in the catalyst of calcining with liquid state.Yet, there is such problem in this case, promptly, because adding ingredient only is distributed on the surface in the surface of catalyst granules and hole, therefore not only the uniformity of granule interior is relatively poor, and since after carrying out dip operation calcined catalyst once more, therefore make operation become complicated, in addition, because other metal ingredient can be dissolved in the dipping solution, therefore also exist to make reactivity worth variation equivalent risk.
On the other hand, in industrial catalyst, not only in the starting stage but also all to keep reactivity worth after long-time the use be very important.Can consider to take out the catalyst of deterioration and the method for replenishing new catalyst.Yet such troublesome poeration can hinder continued operation, and also is disadvantageous economically.In addition, it is also conceivable that catalyst that takes out deterioration and the method for regenerating and replenishing then.Yet the problem of existence is in aforesaid this regeneration, and is more consuming time, needs complex apparatus, and can not regenerate fully.In view of this, need a kind of less catalyst of reduction that can make yield.For example, patent documentation 2 has disclosed a kind of example of catalyst, wherein the Mo-V-Nb-Te catalyst is applied to into the time 1300 hours the gas phase catalysis ammoxidation reaction of propane in, simultaneously the yield of acrylonitrile is remained unchanged basically.Yet the reaction evaluating in the above-mentioned document just for the relative evaluation of short time as 1300 hours, can't fully satisfy performance required in the commercial Application.In addition, for the catalyst that contains Mo-V that is added with rare earth element etc., without any description about its long reaction performance.
Patent documentation 1: the spy opens flat 9-157241 communique
Patent documentation 2: the spy opens flat 11-169716 communique
Patent documentation 3: the spy opens flat 6-228074 communique
Patent documentation 4: the spy opens flat 10-28862 communique
Patent documentation 5: the spy opens the 2000-202293 communique
Patent documentation 6: the spy opens the 2002-301373 communique
Summary of the invention
The problem that the present invention solves
The purpose of this invention is to provide a kind of composite oxide catalysts that contains Mo, V and component X (described component X is at least a element that is selected from alkali earth metal and rare earth element) at least that is used to produce unsaturated acids or unsaturated nitrile, wherein said composite oxide catalysts is a kind of NEW TYPE OF COMPOSITE oxide catalyst, in this composite oxide catalysts, component X is evenly distributed in catalyst granules inside, and the object selectivity is very high.Another object of the present invention provides a kind of by using described composite oxide catalysts that propane or iso-butane are carried out catalytic gas phase oxidation or gas phase catalysis ammoxidation reaction to produce the method for corresponding unsaturated acids or unsaturated nitrile.
The method of dealing with problems
The inventor furthers investigate these problems.Found that, can realize aforementioned purpose by the production method of following composite oxide catalysts, unsaturated acids or unsaturated nitrile and the production method of composite oxide catalyst, thereby finish the present invention.That is, can realize purpose of the present invention by the production method of following composite oxide catalysts, unsaturated acids or unsaturated nitrile and the production method of described composite oxide catalysts.
(1) a kind of composite oxide catalysts, described composite oxide catalysts contains catalyst granules, and described catalyst granules comprises Mo, V, Sb, component X and contains the carrier of silica,
Wherein said component X is at least a element that is selected from alkali earth metal and rare earth element, as described component X with respect to the d of the atomic ratio of 1 Mo atom in the scope of 0.002≤d＜0.01, the atomic ratio of V and Sb is greater than 0 and less than 1,
Wherein said composite oxide catalysts is by described carrier loaded,
Wherein said component X is evenly distributed in the described catalyst granules, and when the cross section to described catalyst granules carried out composition analysis, the dispersion value Dx of the signal intensity ratio of described component X and Si was 0＜D
x＜0.5.
(2) as (1) described composite oxide catalysts, described composite oxide catalysts also comprises Nb.
(3) as (1) or (2) described composite oxide catalysts,
Wherein said component X is at least a element that is selected from Sc, yttrium, La, Ce, Pr and Yb.
(4) as (1) or (2) described composite oxide catalysts,
Wherein said composite oxide catalysts is by with SiO
2Count the silica supported of 20 weight %～60 weight %.
(5) as the purposes of (1) Xiang Zhidi (4) each described composite oxide catalysts in the gas phase catalytic oxidation reaction of propane or iso-butane.
(6) as the purposes of (1) Xiang Zhidi (4) each described composite oxide catalysts in the gas phase catalysis ammoxidation reaction of propane or iso-butane.
(7) a kind of method of producing unsaturated acids or unsaturated nitrile, described method comprise to be used as (1) Xiang Zhidi (4) each described composite oxide catalysts.
(8) a kind of production method as (1) Xiang Zhidi (4) each described composite oxide catalysts, described method comprises:
Silica is mixed into comprises Mo compound, V compound, Sb
2O
3In the mixed liquor of X compound, with preparation raw material mixed liquor;
The described raw material mixed liquor of spray-drying is with preparation dry powder; And calcine described dry powder.
The invention effect
According to the present invention, may be provided in the NEW TYPE OF COMPOSITE oxide catalyst that branch X is uniformly distributed in carrier granular inside.In addition, by using the composite oxide catalysts that obtains according to the present invention, can produce corresponding unsaturated acids or unsaturated nitrile with high yield by propane or iso-butane.
The specific embodiment
To describe the present invention in detail below.At least the composite oxide catalysts that comprises Mo, V and component X (described component X is at least a element that is selected from alkali earth metal and rare earth element) according to the present invention is by containing the carrier loaded of silica, and wherein said component X is evenly distributed in the inside of catalyst granules.As the preferred embodiment of described composite oxide catalysts, can exemplify material by following general formula (1) representative.
Mo
1V
aNb
bY
cX
dO
n (1)
Wherein a, b, c, d and n represent the atomic ratio with respect to 1 Mo atom separately, wherein
A is in the scope of 0.01≤a≤1;
B is in the scope of 0.01≤b≤1;
C is in the scope of 0.01≤c≤1;
The ratio a/c of a and c is in the scope of 0＜a/c＜1;
D is in the scope of 0＜d＜1; And
N is by the numeral that constitutes the atomic valence of metal decision.
In addition, the situation of relevant atomic ratio is as follows: with respect to 1 Mo atom, a to c is preferably 0.1≤a≤0.4,0.01≤b≤0.2 and 0.1≤c≤0.5 respectively.
As component X with respect to the d of the atomic ratio of 1 Mo atom preferably in the scope of 0＜d＜1, more preferably in the scope of 0.001≤d＜0.1, in the scope particularly preferably in 0.002≤d＜0.01.As for the element of component X, be preferably Sr, Ba, Sc, Y (yttrium), La, Ce, Pr and Yb, be preferably Ce especially.
Be preferably 0.01≤c≤0.6 as composition Y with respect to the c of the atomic ratio of 1 Mo atom, more preferably 0.1≤c≤0.4.As for the element of composition Y, preferably use Te and Sb, industrial preferred use Sb.
The composite oxide catalysts that obtains by production method of the present invention is preferably by comprising the carrier loaded supported catalyst of silica as main component.Serve as reasons when containing silica when described composite oxide catalysts,, therefore be suitable for use in the gas phase catalytic oxidation reaction or gas phase catalysis ammoxidation reaction that uses fluidized-bed reactor because its mechanical strength is very high as the carrier loaded catalyst of main component.
In comprising the carrier of silica, with SiO as main component
2The equivalent meter, with respect to the gross weight of the load oxide catalyst of oxide that contains the element that constitutes catalyst and carrier, the content of silica is preferably 20 weight %～60 weight %, more preferably 25 weight %～55 weight %.
In composite oxide catalysts according to the present invention, particular importance a bit be that component X need be evenly distributed in the catalyst granules.Term used herein " equably " is meant that the distribution of component X is not the state that number differs in catalyst granules.Preferably, term " equably " is meant following state: the oxide particle that contains component X more than or equal to 80% (percentage by weight) is present in the catalyst granules as the particulate that particle diameter is less than or equal to 1 μ m.Through after the suitable definition, term " equably " is meant when the cross section to described composite catalyst particle carries out composition analysis, the state of the dispersion value of component X (described component X is at least a element that is selected from alkali earth metal and the rare earth element) and the signal intensity ratio of Si (value that obtains divided by mean value with standard deviation) in 0～0.5 scope.In addition, described dispersion value is expressed as " Dx " at this.
About composition analysis, can use any one common constitutes analysis method, for example SEM-EDX, XPS, SIMS and EPMA etc.Wherein preferably use EPMA.Term used herein " EPMA " is meant the common name (omitting " X ray " sometimes) of electron probe X-ray microanalysis instrument.This analyzer is can be by observing the characteristic X-ray that material radiation accelerated electron beam is obtained, to radiation the tiny area of electron beam (point) carry out the instrument of composition analysis.For cross section,, can obtain the CONCENTRATION DISTRIBUTION of element-specific or form the information that changes by using this EPMA such as solid particles such as catalyst granules or carrier granulars.
In addition, in the present invention, according to the dispersion value (D of the strength ratio of the component X of EPMA and Si
x), be on the cross section of the particle that will measure, follow in the typical catalyst field the particle cross section with the technology that EPMA carries out surface analysis by following mode, measure the value of calculating and obtaining.That is, at first, measure and catalyst granules cross section given position (x, y) the X ray peak strength of relative Si (counting: I
Si) distribution, thereby the Zone Full of catalyst granules cross section is all carried out this measurement.Secondly, with Si in similar methods, measure the X ray peak strength (counting: I of component X
X) distribution, thereby the Zone Full of catalyst granules cross section is carried out this measurement.According to resulting a series of data (x, y, I about Si and component X
Si, I
X), obtain that (x, y) peak strength of locating component X and Si compares I at same position
R(I
R=I
X/ I
Si), then, obtain I
RSimple average value (I
R)
AvAnd standard deviation S, subsequently, will be by using standard deviation S divided by simple average value (I
R)
AvThe value that obtains is as dispersion value (D
x).In the case, simple average value and standard deviation can obtain by common method.
In addition, for preventing from above-mentioned measurement, to cause the uncertainty of data because of the edge effect of particle cross section, preferably the zone of cross section 10% will be accounted on the catalyst granules cross section, promptly foreclose, will account for data on all the other zones of 90% as valid data and be used to calculate from the catalyst granules cross-section center with the corresponding zone of the outer peripheral portion of particle.Certainly, can be only removing the above-mentioned surface analysis that uses EPMA with the inside of the catalyst granules cross section of 10% particle outer peripheral portion The corresponding area in when beginning, then, according to the data of such acquisition, use method same as described above to determine dispersion value D
x
The surface analysis of above-mentioned catalyst granules cross section can be followed the above-mentioned technology of using and carry out in the typical catalyst field, and preferably carries out in mode as described below usually.
That is, at first, the particle that will measure is imbedded in the suitable matrix resin, and carries out integral grinding, comes out up to the cross section of the catalyst granules of so imbedding, and then, the catalyst granules that so exposes cross section is carried out following EPMA test:
(1) position of layout sample makes the cross section of catalyst granules appear in the field of view of EPMA measurement; And
(2) cross section to catalyst granules carries out electron beam irradiation, and the intensity of the Si that record is sent by electron beam irradiation part or the characteristic X-ray of component X then, is carried out surface analysis by the zone that will analyze with electron beam scanning.
Can prepare by commonsense method according to composite oxide catalysts of the present invention, for example can prepare by following three steps:
(I) step of mixed material;
(II) the raw material mixed liquor that is obtained in the drying steps (I), thereby the step of acquisition catalyst precarsor; And
(III) step of the catalyst precarsor that is obtained in the calcining step (II).
Term used herein " mixing " is meant and will constitutes the raw material dissolving of element as catalyst or be distributed in the aqueous solvent.
Term used herein " raw material " is meant the material that uses in the step (I).When preparing according to composite oxide catalysts of the present invention, raw metal is not particularly limited, and can use following compound.
That is, about the raw material of Mo and V, suitable respectively the ammonium heptamolybdate [(NH that uses
4)
6Mo
7O
244H
2O] and ammonium metavanadate [NH
4VO
3].
About the raw material of Nb, can use niobic acid, inorganic niobates and organic niobates.Niobic acid is suitable especially.Niobic acid is by Nb
2O
5NH
2O represents, also can be expressed as the hydrate of niobium hydroxide or niobium oxide.In addition, the mol ratio of preferred dicarboxylic and niobium is 1～4 material solution.About dicarboxylic acids, preferably use oxalic acid.
About the raw material of Sb, be preferably antimony oxide [Sb
2O
3].
About the raw material of Te, be preferably telluric acid [H
6TeO
6].
About the raw material of component X, its material is not particularly limited, and the material of these elements get final product so long as wherein comprise arbitrarily, can use the compound that contains any these elements and with suitable reagent the metal of these elements can be dissolved after material.About containing the arbitrarily compound of these elements, can use ammonium salt, the peroxycarboxylic acid salt of nitrate, carboxylate, carboxylic acid, ammonium salt, ammonium halide salt, halide, acetoacetate and the alkoxide etc. of peroxycarboxylic acid usually.Preferably, can use water-soluble material, for example nitrate or carboxylate etc.
About the raw material of silica, can use Ludox.But also can use silica powder as part or all of silica raw material.Described silica powder is preferably the silica powder by the high temperature process preparation.In addition, more preferably silica powder is dispersed in the water, uses then.
To describe below the preparation catalyst according to the invention preferred embodiment, comprising step (I) to (III).
(step I: the step of mixed material)
The composition that can become other raw material of Mo compound, V compound and X composition and selection is as required added in the entry heating then, thereby preparation mixed liquor (A).In the case, can make internal tank is nitrogen atmosphere.When comprising Nb, Nb compound and dicarboxylic acids are added in the entry heating when stirring then, thereby preparation mixed liquor (B
0).In addition, can be to mixed liquor (B
0) the middle hydrogen peroxide that adds, thereby preparation mixed liquor (B).In the case, H
2O
2/ Nb (mol ratio) is preferably 0.5～20, is preferably 1～10 especially.Can be to mixed liquor (B
0) or (B) in add oxalic acid again.
Form according to purpose, with mixed liquor (A), mixed liquor (B
0) or suitably mixing of mixed liquor (B), to obtain the raw material mixed liquor.
When the catalyst that is used for ammoxidation according to the present invention is silica supported catalyst, then prepares the raw material mixed liquor and make it comprise Ludox.Can be to wherein suitably adding Ludox.
(Step II: drying steps)
By the raw material mixed liquor that obtains in the spray drying process drying steps (I), thereby obtain dry powder.Spraying in the spray drying process can adopt centrifugation, two-fluid spray nozzle mode or high pressure nozzle mode to carry out.About the drying thermal source, can use air by heating such as steam or electric heaters.The temperature of hot-air in the drier porch is preferably 150 ℃～300 ℃.
(Step II I: calcining step)
Dry powder by obtaining in the calcining drying steps can obtain oxide catalyst.Calcining is carried out in the atmosphere of inert gases of for example basic oxygen-free gas such as nitrogen, argon gas or helium at (preferably under 600 ℃～700 ℃) under 500 ℃～800 ℃, preferably makes the inert gas circulation simultaneously.Calcination time is 0.5 hour～20 hours, preferred 1 hour～8 hours.
Can calcine by using rotary kiln, tunnel cave, tube furnace, the calcining furnace that flows etc.Calcining can be carried out repeatedly.
Before carrying out calcining step, preferably with dry powder precalcining 1 hour～5 hours under 200 ℃～400 ℃, under atmospheric environment or circulation of air.
In the presence of the oxide catalyst that so prepares, make propane or iso-butane carry out catalytic gas phase oxidation or gas phase catalysis ammoxidation reaction, thereby prepare corresponding unsaturated acids or unsaturated nitrile.
The raw material of propane of being supplied or iso-butane and ammonia needs not to be highly purified, uses the gas of technical grade purity to get final product.
About oxygen source, can use air, be rich in the air or the purity oxygen of oxygen.In addition, can supply helium, argon gas, carbon dioxide, water vapour, nitrogen etc. as diluent gas.
The catalytic gas phase oxidation of propane or iso-butane can carry out under the following conditions:
The oxygen of supplying for reaction and the mol ratio of propane or iso-butane are 0.1～6, are preferably 0.5～4;
Reaction temperature is 300 ℃～500 ℃, is preferably 350 ℃～450 ℃;
Reaction pressure is 5 * 10
4Pa～5 * 10
5Pa is preferably 1 * 10
5Pa～3 * 10
5Pa;
Be 0.1～10 (secg/cc) time of contact, is preferably 0.5～5 (secg/cc).In the present invention, can determine by following formula time of contact:
Time of contact (secg/cc)=(W/F) * 273/ (273+T)
Wherein W, F and T are defined as follows:
W=catalyst loading (g);
F=standard state (0 ℃, 1.013 * 10
5Pa) flow velocity (Ncc/sec) of mixed raw material gas under; And
The T=reaction temperature (℃).
The gas phase catalysis ammoxidation of propane or iso-butane can be carried out under the following conditions:
The oxygen of supplying for reaction and the mol ratio of propane or iso-butane are 0.1～6, are preferably 0.5～4;
The ammonia of supplying for reaction and the mol ratio of propane or iso-butane are 0.3～1.5, are preferably 0.7～1.2;
Reaction temperature is 350 ℃～500 ℃, is preferably 380 ℃～470 ℃;
Reaction pressure is 5 * 10
4Pa～5 * 10
5Pa is preferably 1 * 10
5Pa～3 * 10
5Pa; And
Be 0.1～10 (secg/cc) time of contact, is preferably 0.5～5 (secg/cc).
About reaction method, can adopt such as any one conventional methods such as fixed bed process, fluidized bed process and moving bed methods, wherein because fluidized bed process is easy to remove reaction heat, the therefore preferred fluidized bed process that adopts.
In addition, can be single current according to reaction of the present invention, also can be circulating.
Embodiment
Illustrate according to composite oxide catalysts of the present invention below with reference to the embodiment that produces described catalyst with by the preparation embodiment of gas phase catalysis ammoxidation reaction by propane production acrylonitrile, but the present invention is not limited thereto, only otherwise breaking away from main idea of the present invention gets final product.
The evaluation of the performance of the ammoxidation reaction of propane is a foundation with the analysis result to reacting gas, simultaneously will be by the selection rate of the conversion of propane of following formula representative and acrylonitrile as index:
[formula 1]
Conversion of propane (%)
=(molal quantity of the propane of reaction)/(molal quantity of the propane of supply) * 100
The selection rate of acrylonitrile (%)
=(molal quantity of the acrylonitrile of generation)/(molal quantity of the propane of reaction) * 100
(preparation of niobium mixed liquor)
Open the specification of flat 11-253801 communique according to the spy, use following method to prepare the mixed liquor of niobium.
In 2552g water, add 352g with Nb
2O
5Meter contains the niobic acid and the 1344g oxalic acid dihydrate [H of the niobium of 80 weight %
2C
2O
42H
2O].As the oxalic acid of charging and the mol ratio of niobium is 5.03, and the concentration of charging niobium is 0.50 (mol-Nb/Kg/ solution).Under agitation, gained solution was heated 1 hour at 95 ℃, thereby the mixed liquor of niobium has been dissolved in acquisition.Leave standstill this mixed liquor and, carry out suction filtration then removing solid constituent, thereby obtain uniform niobium mixed liquor with ice-cooled.By following analysis, the mol ratio of finding this niobium mixed liquor mesoxalic acid and niobium is 2.52.
Accurately this niobium mixed liquor of weighing 10g puts it in the crucible, 95 ℃ of dried overnight, and 600 ℃ of heat treatments 1 hour, thereby obtain 0.8228g Nb
2O
5Found that according to this niobium concentration is 0.618 (mol-Nb/Kg/ solution).
Accurately this niobium mixed liquor of weighing 3g is put into the glass beaker that volume is 300ml, and adds about 200ml temperature and be about 80 ℃ hot water, adds 1: 1 the sulfuric acid of 10ml then.Use 1/4N KMnO
4Solution, on the thermal agitation device when temperature is remained 70 ℃ titration gained mixed liquor under agitation.Will be based on KMnO
4The rose pink duration be defined as terminal point more than or equal to about 30 seconds point.Calculate by titer according to following formula, as a result concentration of oxalic acid be 1.558 (mol-oxalic acid/Kg):
2KMnO
4+3H
2SO
4+5H
2C
2O
4→K
2SO
4+2MnSO
4+10CO
2+8H
2O
The niobium mixed liquor that so obtains is used as below with employed niobium mixed liquor (B in the Preparation of Catalyst of describing
0).
Embodiment 1
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Ce
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression:
In 4584g water, add 915.0g ammonium heptamolybdate [NH
4)
6Mo
7O
244H
2O], 127.3g ammonium metavanadate [NH
4VO
3], 188.8g antimony oxide [Sb
2O
3] and 11.25g cerous nitrate hexahydrate [Ce (NO
3)
36H
2O], when stirring,, thereby obtain mixed liquor A-1 90 ℃ of heating 2.5 hours.
To 754.6g niobium mixed liquor (B
0) in add the H that 105.8g contains 30 weight %
2O
2Hydrogenperoxide steam generator, and at room temperature mixed 10 minutes, thus preparation mixed liquid B-1.
After the mixed liquor A-1 that so obtains is cooled to 70 ℃, contain the SiO of 30.2 weight % to wherein adding 2980g
2Ludox, contain the H of 30 weight % to wherein adding 220.4g again
2O
2Hydrogenperoxide steam generator, then, the gained mixed liquor continue was stirred 1 hour at 50 ℃.Next, in the gained mixed liquor, add mixed liquid B-1, thereby obtain the raw material mixed liquor.
In centrifugal spray drier, supply with the raw material mixed liquor that so obtains and carry out drying, thereby obtain microspheroidal dry powder.The temperature at the entrance and exit place of drier is respectively 210 ℃ and 120 ℃.
It is in 3 inches the stainless steel calcining tube that the dry powder that 480g is so obtained is filled to diameter, then 640 ℃, be calcining 2 hours in this pipe of rotation in the nitrogen stream of 5.0NL/min at flow velocity, thereby obtain catalyst.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out the analyzing crystal of Si when measuring, can use LiF (lithium fluoride) (using 200 faces).When measuring Ce, can use PET (PETG) (using 002 face).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
The catalyst that 35g is so prepared is filled in the Wei Ke that internal diameter is 25mm (Vycor) the glass fluid bed reaction tube.In reaction temperature is that 440 ℃, reaction pressure are under the condition of atmospheric pressure, and with propane: ammonia: oxygen: the mol ratio of helium is 1: 1: 3: 18 admixture of gas is being time of contact that the speed of 2.8 (secg/cc) adds in the reaction tube.The result that the reaction beginning obtained after 5 hours is as shown in table 1, and the result who obtains after 1200 hours and 2400 hours is as shown in table 2.
Comparative example 1
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Ce
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression:
In 4602g water, add 918.5g ammonium heptamolybdate [(NH
4)
6Mo
7O
244H
2O], 127.8g ammonium metavanadate [NH
4VO
3], 189.6g antimony oxide [Sb
2O
3] and 4.46g cerium hydroxide [Ce (OH)
4], when stirring, heated 2.5 hours, thereby obtain mixed liquor A-2 at 90 ℃.To 757.5g niobium mixed liquor (B
0) in add 106.2g and contain 30 weight %H
2O
2Hydrogenperoxide steam generator, and at room temperature mixed 10 minutes, thus preparation mixed liquid B-2.
After the mixed liquor A-2 that so obtains is cooled to 70 ℃, contain the SiO of 30.2 weight % to wherein adding 2980g
2Ludox.Next, in the gained mixed liquor, add mixed liquid B-2, thereby obtain the raw material mixed liquor.
In centrifugal spray drier, supply with the raw material mixed liquor that so obtains and carry out drying, thereby obtain microspheroidal dry powder.The temperature at the entrance and exit place of drier is respectively 210 ℃ and 120 ℃.
It is in 3 inches the stainless steel calcining tube that the dry powder that 480g is so obtained is filled to diameter, then 640 ℃, be calcining 2 hours in this pipe of rotation in the nitrogen stream of 5.0NL/min at flow velocity, thereby obtain catalyst.
(composition analysis)
Use the method identical, the oxide catalyst of acquisition like this is carried out the EMPA measurement with embodiment 1.The result is as shown in table 1.
(ammoxidation reaction of propane)
The catalyst that 35g is so prepared is filled in the Vycor glass fluidized-bed reaction pipe that internal diameter is 25mm.In reaction temperature is that 440 ℃, reaction pressure are under the condition of atmospheric pressure, and with propane: ammonia: oxygen: the mol ratio of helium is 1: 1: 3: 18 admixture of gas is being time of contact that the speed of 2.8 (secg/cc) adds in the reaction tube.The result that the reaction beginning obtained after 5 hours is as shown in table 1, and the result who obtains after 1200 hours and 2400 hours is as shown in table 2.
Comparative example 2
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Ce
0.05O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.Except adding 44.6g cerium hydroxide [Ce (OH)
4] as outside the cerium raw material, repeat the preparation process identical with embodiment 1.
(composition analysis)
Use the method identical, the oxide catalyst of acquisition like this is carried out the EMPA measurement with embodiment 1.The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result that the reaction beginning obtained after 5 hours is as shown in table 1, and the result who obtains after 1200 hours and 2400 hours is as shown in table 2.
Embodiment 2
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Ce
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.In 4584g water, add 915.0g ammonium heptamolybdate [(NH
4)
6Mo
7O
244H
2O], 127.3g ammonium metavanadate [NH
4VO
3], 188.8g antimony oxide [Sb
2O
3] and 11.25g cerous nitrate hexahydrate [Ce (NO
3)
36H
2O], when stirring,, thereby obtain mixed liquor A-4 90 ℃ of heating 2.5 hours.
To 754.6g niobium mixed liquor (B
0) in add 105.8g and contain 30 weight %H
2O
2Hydrogenperoxide steam generator, and at room temperature mixed 10 minutes, thus preparation mixed liquid B-4.
After the mixed liquor A-4 that so obtains is cooled to 70 ℃, contain 30.2 weight %SiO to wherein adding 1490g
2Ludox, contain 30 weight %H to wherein adding 220.4g again
2O
2Hydrogenperoxide steam generator, then, continue to stir 1 hour at 50 ℃.Next, in the gained mixed liquor, add mixed liquid B-4 successively and wherein 450g powder silica is dispersed in dispersion liquid in the 6300g water, thereby obtain the raw material mixed liquor.
In centrifugal spray drier, supply with the raw material mixed liquor that so obtains, thereby obtain microspheroidal dry powder.The temperature at the entrance and exit place of drier is respectively 210 ℃ and 120 ℃.
It is in 3 inches the stainless steel calcining tube that the dry powder that 480g is so obtained is filled to diameter, then 640 ℃, be calcining 2 hours in this pipe of rotation in the nitrogen stream of 5.0NL/min at flow velocity, thereby obtain catalyst.
(composition analysis)
Use the method identical, the oxide catalyst of acquisition like this is carried out the EMPA measurement with embodiment 1.The result is as shown in table 1.
(ammoxidation reaction of propane)
The catalyst that 35g is so prepared is filled in the Vycor glass fluidized-bed reaction pipe that internal diameter is 25mm.In reaction temperature is that 440 ℃, reaction pressure are under the condition of atmospheric pressure, and with propane: ammonia: oxygen: the mol ratio of helium is 1: 1: 3: 18 admixture of gas is being time of contact that the speed of 2.8 (secg/cc) adds in the reaction tube.The result is as shown in table 1.
Embodiment 3
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Sc
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.Except adding 7.85g scandium nitrate tetrahydrate [Sc (NO
3)
34H
2O] replace outside the cerous nitrate, repeat the preparation process identical with embodiment 2.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out Si and the Sc analyzing crystal when measuring, can use LiF (lithium fluoride) (using 200 faces).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result is as shown in table 1.
Embodiment 4
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Y
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.Except adding 9.92g yttrium nitrate hexahydrate [Y (NO
3)
36H
2O] replace outside the cerous nitrate hexahydrate, repeat the preparation process identical with embodiment 2.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out the analyzing crystal of Si when measuring, can use LiF (lithium fluoride) (using 200 faces).When measuring Y, can use PET (PETG) (using 002 face).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result that the reaction beginning obtained after 5 hours is as shown in table 1, and the result who obtains after 1200 hours and 2400 hours is as shown in table 2.
Embodiment 5
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25La
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.Except adding 11.21g lanthanum nitrate hexahydrate [La (NO
3)
36H
2O] replace outside the cerous nitrate hexahydrate, repeat the preparation process identical with embodiment 2.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out Si and the La analyzing crystal when measuring, can use LiF (lithium fluoride) (using 200 faces).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result is as shown in table 1.
Embodiment 6
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Pr
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.Except adding 11.27g praseodymium nitrate hexahydrate [Pr (NO
3)
36H
2O] replace outside the cerous nitrate hexahydrate, repeat the preparation process identical with embodiment 2.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out Si and the Pr analyzing crystal when measuring, can use LiF (lithium fluoride) (using 200 faces).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result is as shown in table 1.
Embodiment 7
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Yb
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.Except adding 10.70g ytterbium nitrate trihydrate [Yb (NO
3)
33H
2O] replace outside the cerous nitrate hexahydrate, repeat the preparation process identical with embodiment 2.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out Si and the Yb analyzing crystal when measuring, can use LiF (lithium fluoride) (using 200 faces).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result is as shown in table 1.
Embodiment 8
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Sr
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.Except adding 5.48g strontium nitrate [Sr (NO
3)
2] replace outside the cerous nitrate hexahydrate, repeat the preparation process identical with embodiment 2.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out Si and the Sr analyzing crystal when measuring, can use LiF (lithium fluoride) (using 200 faces).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result is as shown in table 1.
Embodiment 9
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Ba
0.005O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.Except adding 6.77g barium nitrate [Ba (NO
3)
2] replace outside the cerous nitrate hexahydrate, repeat the preparation process identical with embodiment 2.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out Si and the Ba analyzing crystal when measuring, can use LiF (lithium fluoride) (using 200 faces).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result that the reaction beginning obtained after 5 hours is as shown in table 1, and the result who obtains after 1200 hours and 2400 hours is as shown in table 2.
Embodiment 10
(Preparation of catalysts)
Prepare the feed composition formula by Mo by following method
1V
0.21Nb
0.09Sb
0.25Ce
0.05O
n/ 45.0 weight %-SiO
2The oxide catalyst of expression.
Except the cerous nitrate hexahydrate that will add is thus changed into the 112.5g by 11.25g, repeat the preparation process identical with embodiment 2.
(composition analysis)
Carrying out EPMA by the 1600 pairs of oxide catalysts that so obtain of EPMA that use Shimadzu Seisakusho Ltd. to make measures.Measuring condition is as follows: accelerating potential: 0kV～30kV; Step-length: 1.0 μ m; Spot diameter: 1.0 μ m.As carrying out the analyzing crystal of Si when measuring, can use LiF (lithium fluoride) (using 200 faces).When measuring Ce, can use PET (PETG) (using 002 face).As for detector, can use Kr-Exatron detector (proportional counter tube).The result is as shown in table 1.
(ammoxidation reaction of propane)
Use the method identical, carry out the ammoxidation reaction of propane at the oxide catalyst of acquisition like this with embodiment 1.The result that the reaction beginning obtained after 5 hours is as shown in table 1, and the result who obtains after 1200 hours and 2400 hours is as shown in table 2.
[table 1]
| X composition raw material | Dispersion value | AN yield (%) after 5 hours | |
| Embodiment 1 | Cerous nitrate hexahydrate | 0.15 | 53.8 |
| Comparative example 1 | Cerium hydroxide | 0.81 | 49.5 |
| Comparative example 2 | Cerium hydroxide | 0.95 | 49.8 |
| X composition raw material | Dispersion value | AN yield (%) after 5 hours | |
| Embodiment 2 | Cerous nitrate hexahydrate | 0.13 | 54.3 |
| Embodiment 3 | The scandium nitrate tetrahydrate | 0.14 | 53.1 |
| Embodiment 4 | The yttrium nitrate hexahydrate | 0.16 | 52.9 |
| Embodiment 5 | The lanthanum nitrate hexahydrate | 0.16 | 52.8 |
| Embodiment 6 | The praseodymium nitrate hexahydrate | 0.12 | 53.6 |
| Embodiment 7 | The ytterbium nitrate trihydrate | 0.13 | 53.5 |
| Embodiment 8 | Strontium nitrate | 0.15 | 52.4 |
| Embodiment 9 | Barium nitrate | 0.16 | 52.5 |
| Embodiment 10 | Cerous nitrate hexahydrate | 0.44 | 50.3 |
[table 2]
| AN yield (%) after 1200 hours | AN yield (%) after 2400 hours | |
| Embodiment 1 | 53.5 | 53.1 |
| Comparative example 1 | 35.0 | 32.5 |
| Embodiment 4 | 54.1 | 53.9 |
| Embodiment 9 | 52.2 | 51.8 |
| Embodiment 10 | 47.1 | 45.2 |
Though describe the present invention in detail, it will be apparent to one skilled in the art that and to carry out various changes and modifications and can not break away from the spirit and scope of the present invention with reference to its specific embodiments.
The present invention is based on Japanese patent application 2004-236956 that submitted on August 17th, 2004 and the Japanese patent application 2004-236957 that submitted on August 17th, 2004, their content is hereby incorporated by.
Industrial applicibility
Therefore, can advantageously be applied in the following industrial processes according to composite oxide catalysts of the present invention: produce corresponding unsaturated acids or corresponding unsaturated nitrile by propane or iso-butane being carried out gas phase catalytic oxidation reaction or gas phase catalysis ammoxidation reaction.
Claims (8)
1. composite oxide catalysts, described composite oxide catalysts contains catalyst granules, the carrier that described catalyst granules comprises Mo, V, Sb and component X and contains silica,
Wherein said component X is at least a element that is selected from alkali earth metal and rare earth element, as described component X with respect to the d of the atomic ratio of 1 Mo atom in the scope of 0.002≤d＜0.01, the atomic ratio of V and Sb is greater than 0 and less than 1,
Wherein said component X is evenly distributed in the described catalyst granules, and when the cross section to described catalyst granules carried out composition analysis, the dispersion value Dx of the signal intensity ratio of described component X and Si was 0＜D
x＜0.5.
2. composite oxide catalysts as claimed in claim 1, described composite oxide catalysts also comprises Nb.
3. composite oxide catalysts as claimed in claim 1 or 2,
Wherein said component X is at least a element that is selected from Sc, yttrium, La, Ce, Pr and Yb.
4. composite oxide catalysts as claimed in claim 1 or 2,
Wherein with respect to the gross weight of described composite oxide catalysts, the content of described silica is with SiO
2Equivalent is counted 20 weight %～60 weight %.
5. as the purposes of each described composite oxide catalysts of claim 1 to 4 in the gas phase catalytic oxidation reaction of propane or iso-butane.
6. as the purposes of each described composite oxide catalysts of claim 1 to 4 in the gas phase catalysis ammoxidation reaction of propane or iso-butane.
7. method of producing unsaturated acids or unsaturated nitrile, described method comprise to be used as each described composite oxide catalysts of claim 1 to 4.
8. production method as each described composite oxide catalysts of claim 1 to 4, described method comprises:
Silica is mixed into comprises Mo compound, V compound, Sb
2O
3In the mixed liquor of X compound, with preparation raw material mixed liquor;
The described raw material mixed liquor of spray-drying is with preparation dry powder; And calcine described dry powder.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP236957/2004 | 2004-08-17 | ||
| JP2004236957A JP5078222B2 (en) | 2004-08-17 | 2004-08-17 | Composite oxide catalyst |
| JP236956/2004 | 2004-08-17 | ||
| JP2004236956A JP5263855B2 (en) | 2004-08-17 | 2004-08-17 | Catalyst made of complex oxide |
| PCT/JP2005/014919 WO2006019078A1 (en) | 2004-08-17 | 2005-08-15 | Catalyst composed of complex oxide |
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| JP5596979B2 (en) * | 2007-02-16 | 2014-10-01 | イネオス ユーエスエイ リミテッド ライアビリティ カンパニー | Method for ammoxidation of propane and isobutane using mixed metal oxide catalyst |
| US10179763B2 (en) | 2014-03-06 | 2019-01-15 | Asahi Kasei Kabushiki Kaisha | Oxide catalyst and method for producing same, and method for producing unsaturated nitrile |
| KR101837874B1 (en) * | 2014-03-31 | 2018-03-12 | 아사히 가세이 가부시키가이샤 | Method for producing oxide catalyst and method for producing unsaturated nitrile |
| CN106881103A (en) * | 2015-12-15 | 2017-06-23 | 上海华谊新材料有限公司 | The application method of composite oxide catalysts |
| WO2021153174A1 (en) * | 2020-01-31 | 2021-08-05 | 旭化成株式会社 | Composition for catalyst production, production method of composition for catalyst production, and production method for producing oxide catalyst |
| CN114471596B (en) * | 2020-10-27 | 2023-09-29 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for preparing catalyst |
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| CN1216721A (en) * | 1997-10-15 | 1999-05-19 | 旭化成工业株式会社 | Ammoxidation catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane by ammoxidation |
| JP2002316052A (en) * | 2001-04-24 | 2002-10-29 | Mitsubishi Chemicals Corp | Method for manufacturing complex metallic oxide catalyst |
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| JP4209007B2 (en) * | 1997-10-15 | 2009-01-14 | 旭化成ケミカルズ株式会社 | Catalyst for acrylonitrile or methacrylonitrile production |
| JP4187856B2 (en) * | 1999-01-19 | 2008-11-26 | 旭化成ケミカルズ株式会社 | Catalyst and method for producing unsaturated nitrile using the same |
| JP2002292284A (en) * | 2001-04-03 | 2002-10-08 | Mitsubishi Chemicals Corp | Compound metal oxide catalyst and method for gaseous phase catalytic oxidizing reaction using the same |
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| CN1216721A (en) * | 1997-10-15 | 1999-05-19 | 旭化成工业株式会社 | Ammoxidation catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane by ammoxidation |
| JP2002316052A (en) * | 2001-04-24 | 2002-10-29 | Mitsubishi Chemicals Corp | Method for manufacturing complex metallic oxide catalyst |
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