CN101279252B - Catalysts for the ammoxidation of alkanes - Google Patents
Catalysts for the ammoxidation of alkanes Download PDFInfo
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- CN101279252B CN101279252B CN2007100390411A CN200710039041A CN101279252B CN 101279252 B CN101279252 B CN 101279252B CN 2007100390411 A CN2007100390411 A CN 2007100390411A CN 200710039041 A CN200710039041 A CN 200710039041A CN 101279252 B CN101279252 B CN 101279252B
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a catalyst for alkane ammoxidation, which mainly aims at solving the problems of bad stability of the catalyst caused by that stibium requires circumfluence and Te is easy to volatilize in the prior art. The invention adopts the catalyst which is composed of the silicon dioxide carrier and oxide expressed in atomic ratio by the following general formula MoVaNbbTecOx, wherein, the preparation environment is changed by adjusting pH value by adding with acid in the process of preparation. Firstly the corresponding salt or oxide of Mo and Te is dissolved, then the solution of the corresponding salt or oxide of V and Nb is respectively added and acid with required amount is added for adjusting the pH value of the mixed solution, and at last silicasol with the required amount is added for preparing the catalyst. The technical proposal better solves the problems. The catalyst of the invention has the advantages of excellent stability of oxidation and reduction, low reaction temperature, clean reaction product and being capable of keeping higher yield for a long time, thus being suitable for preparing unsaturated nitriles with alkane ammoxidation in industrial production.
Description
Technical field
The present invention relates to a kind of catalyst that is used for alkane ammoxidation reaction, especially about the catalyst of propane ammoxidation acrylonitrile production and iso-butane prepared by ammoxidation methacrylonitrile.
Background technology
Although the most of ammoxidation of propylene technology that adopts BP/Sohio of the production of acrylonitrile at present, but along with the variation in petrochemical industry market and going deep into of alkane selective oxidation research, because propane and the price difference XOR iso-butane of propylene and the price variance of isobutene, come into one's own day by day by the process route of propane ammoxidation acrylonitrile production or iso-butane prepared by ammoxidation methacrylonitrile.
For obtaining the propane ammoxidation acrylonitrile production catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.Previously attempt to develop a kind of propane ammoxidation is generated the effective ways of acrylonitrile, the result is that yield is not high enough, perhaps must add halogen and make co-catalyst in the charging thing.In the charging thing, must add halogen and do in the co-catalyst method, not only require reactor to make, and require the co-catalyst quantitative recovery by extraordinary resistant material.This surcharge has been offset the advantage of propane/propylene price difference, has hindered these catalyst in industrial application.
Patent CN1029397C discloses certain O composite metallic oxide catalyst that contains V, Sb, W and some optional elements, is applied in C
3-C
4Alkane ammoxidation is produced α, the method of alpha, beta-unsaturated nitriles and alkene, wherein the average valence mumber of Sb be higher than+3, the average valence mumber of V is lower than+and 5, the method is used in propane ammoxidation when producing acrylonitrile, in the reactant steam need be arranged, severe reaction conditions is brought influence to later industrialized plant capacity.
Patent CN1062306A discloses the catalyst system of alkane ammoxidation; adopt a kind of granulate mixture of two kinds of catalyst components; first kind of catalyst component is effective especially to quickening by alkane generation unsaturated nitrile and alkene; second kind of catalyst component is effective especially to the conversion of unsaturated nitrile to quickening alkene; the method system complexity, acrylonitrile yield is lower.
Patent CN1178903C discloses the vanadium-antimony-oxide substrate catalyst that the molybdenum that is used for selective paraffin ammoxidation helps catalysis, with the catalyst after the moistening equably calcining of the aqueous solution that contains molybdenum, dry, wash with isobutanol again after the calcining, the method preparation process complexity, in preparation process, wash with isobutanol, and then dry, operate dangerous property.Patent CN1087734C discloses a kind of method that is prepared acrylonitrile or methacrylonitrile by propane or iso-butane through ammoxidation, catalyst comprises that composite oxides and load thereon have the silica supports of composite oxides, and wherein composite oxides are expressed as:
Mo
1Te
aV
bNb
cX
dO
n
Wherein X is at least a element that is selected from tantalum, tungsten, chromium, titanium, zirconium, antimony, bismuth, tin, hafnium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, zinc, aluminium, gallium, indium, thallium, phosphorus and alkaline-earth metal.
Above-mentioned catalyst can obtain higher acrylonitrile yield, but contains volatile element Te in the catalyst activity component, need add Te in reaction, and stability is bad, thereby does not have enough life-spans to make this method uneconomical.
Patent CN1174801C discloses a kind of formula Mo that contains
1V
aNb
bX
cZ
yQ
fO
n, wherein X is at least a element that is selected from Te and Sb; Y is at least a element that is selected from Al and W; Z is at least a element that is selected from the element that can be individually formed the oxide with rutile structure, and has the source use of the Z oxide of rutile structure as the Z of preparation catalyst; Q is at least a element that is selected from titanium, tin, germanium, lead, tantalum, ruthenium, rhenium, rhodium, iridium, platinum, chromium, manganese, technetium, osmium, iron, arsenic, cerium, cobalt, magnesium, nickel and zinc; And the Q compound that does not have rutile structure uses as the source of the Q of preparation catalyst.The catalyst acrylonitrile yield that this method makes is higher, but forms complicatedly, and the ingredient requirement height makes that industrial production repeatability is bad and seems uneconomical.
Patent CN1771085A discloses a kind of catalytic gas phase oxidation of propane or iso-butane or oxide catalyst of gas phase catalysis ammoxidation of being used for, it comprises with the specific atoms ratio and contains molybdenum (Mo), vanadium (V), niobium (Nb) and antimony (Sb) as the oxide of component, uses H
2O
2Adjust the percent reduction and the specific area of methods such as the oxidation state control catalyst of oxide.The catalyst that this method makes can stably be produced unsaturated carboxylic acid or unsaturated nitrile with higher yields for a long time, but the controlled condition harshness makes Catalyst Production be difficult for.
All exist corresponding salt of Sb or oxide to reflux among the existing preparation method, adopt the V of severe toxicity
2O
5Be raw material, or the catalyst activity component that makes is volatile and cause problems such as catalyst stability is bad, directly causes preparation environment instability in the preparation process at last, makes that corresponding unsaturated nitrile yield is not high or catalyst stability is bad and seem uneconomical.
Summary of the invention
Technical problem to be solved by this invention is to overcome all to exist Sb to reflux in the above-mentioned document to cause complicated process of preparation and yield not high, and the volatile bad problem of catalyst stability that causes of Te provides a kind of catalyst of new alkane ammoxidation reaction.This catalyst has advantages of excellent oxidation-reduction stability, and reaction temperature is low, and product cleans and can keep for a long time the advantage of higher yields.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for alkane ammoxidation reaction, by silica supports be expressed as the oxide of following general formula with atomic ratio measuring:
MoV
aNb
bTe
cO
x
Wherein, the span of a is 0.1～1.0;
The span of b is 0.01～1.0;
The span of c is 0.01～1.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
The consumption of carrier silica is 30～70% of catalytic amount by weight percentage in the catalyst;
This Preparation of catalysts comprises the steps:
1) with aequum Mo and corresponding salt of Te or the oxide solution (I) of making soluble in water;
2) with corresponding salt of aequum V or the oxide solution (II) of making soluble in water;
3) with corresponding salt of aequum Nb or the oxide solution (III) of making soluble in water;
4) aequum is selected from HNO
3Or H
2SO
4In at least a acid solution (IV) of making soluble in water;
5) solution (II) is joined in the solution (I), successively solution (III) and solution (IV) are joined wherein again, regulating mixed pH value of solution value is 1～4, the Ludox that adds aequum at last, make the slurry of catalyst, this slurry stirs down evaporation at 80～180 ℃ and obtains viscous paste always, and is dry then, temperature be in 400～800 ℃ the inert atmosphere roasting 0.5～8 hour the alkane ammoxidation catalyst.
In the technique scheme, mixed pH value of solution value preferable range is 1～3, and catalyst sintering temperature preferable range is 500～700 ℃, and the calcination atmosphere preferred version is a nitrogen, and the roasting time preferable range is 1～4 hour.
The raw material of preparation catalyst of the present invention is:
The most handy corresponding oxide of molybdenum component in the catalyst or its ammonium salt, the most handy corresponding oxide of vanadium component or its ammonium salt, the most handy corresponding oxide of tellurium component, hydroxide or its ammonium salt in the catalyst; Niobium can be with its oxide, hydroxide, nitrate or oxalates.
For reaching above-mentioned purpose and advantage, method of the present invention also is included in gas phase makes the alkane that is selected from propane and iso-butane and molecular oxygen and ammonia carry out catalytic reaction, wherein reactant reacts at reaction zone and catalyst, preparation α, alpha, beta-unsaturated nitriles, acrylonitrile or methacrylonitrile, desired molecule oxygen can be used pure oxygen from technical standpoint in the raw material components, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Entering the ammonia of fixed bed reactors and the mol ratio of propane is between 0.8～1.5, is preferably 1.0～1.3.The mol ratio of air and propane is 8～16, is preferably 9.0～14.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fixing bed bioreactor, reaction temperature was 370～450 ℃, was preferably 390～440 ℃.
Though catalyst of the present invention is formed simple, but owing to improved the Preparation of catalysts method, in preparation process, regulate the pH value of mixed solution, thereby make that generating crystal between Te, the Mo obtains good catalyst stability, the catalyst that availability can be good by adding acid.Catalyst of the present invention has to be formed simply, and needed raw material is easy to get, good reproducibility, and the catalyst yield height that makes has good stability, and reaction temperature is low, has obtained better technical effect.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 8 millimeters fixed bed reactors.Loaded catalyst 2.0 gram, 405 ℃ of reaction temperatures, reaction pressure are normal pressure, raw material proportioning (mole) is a propane: ammonia: air=1: 1.2: 10, catalyst time of contact is 1.2 gram-second/milliliters.
Conversion of propane, acrylonitrile selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment, but the present invention is not limited by following examples.
The specific embodiment
[embodiment 1]
15.0 gram ammonium heptamolybdates and 4.46 gram telluric acids are dissolved in the 69.2 gram hot water, make solution (I); 3.06 gram ammonium metavanadates are dissolved in the 60.0 gram hot water, make solution (II); 5.78 gram niobium oxalates are dissolved in the 16.0 gram hot water, make solution (III); Getting the 1ml98% concentrated sulfuric acid is dissolved in 9 grams and makes solution (IV) in the water.Under agitation solution (I) is joined in the solution (II), add solution (III) and solution (IV) more successively, the pH value of mixed solution is 1, add 50 gram weight concentration at last and be 40% Ludox, make the slurry of catalyst, this slurry is stirred evaporation down at 90 ℃ obtain viscous paste always, dry then, grind, roasting is 2 hours in 600 ℃ of nitrogen atmospheres, can get propane ammoxidation catalyst Mo
lV
0.31Nb
0.22Te
0.23O
x+ 50%SiO
2, get 20～40 orders behind the compressing tablet and carry out the fixed bed micro anti-evaluation.
[comparative example 1]
15.0 gram ammonium heptamolybdates and 4.46 gram telluric acids are dissolved in the 69.2 gram hot water, make solution (I); 3.06 gram ammonium metavanadates are dissolved in the 60.0 gram hot water, make solution (II); 5.78 gram niobium oxalates are dissolved in the 16.0 gram hot water, make solution (III).Under agitation solution (I) is joined in the solution (II), add solution (III) again, add 50 gram weight concentration at last and be 40% Ludox, make the slurry of catalyst, this slurry is stirred evaporation down at 90 ℃ obtain viscous paste always, dry then, grind, roasting is 2 hours in 600 ℃ of nitrogen atmospheres, can get propane ammoxidation catalyst Mo
lV
0.31Nb
0.22Te
0.23O
x+ 50%SiO
2, get 20～40 orders behind the compressing tablet and carry out the fixed bed micro anti-evaluation.
[embodiment 2～6 and comparative example 2～3]
Adopt method substantially the same manner as Example 1 preparation to have the different catalyst of forming in the following table, and under following reaction condition, carry out the reaction of propane ammoxidation generation acrylonitrile, specifically change and the results are shown in Table 1 with prepared catalyst.
The reaction condition of the foregoing description and comparative example is:
Internal diameter is 8 millimeters fixed bed reactors
405 ℃ of reaction temperatures
The reaction pressure atmospheric pressure
Loaded catalyst 2.0 grams
Catalyst gram-second/milliliter times of contact 1.2
Raw material proportioning (mole) propane/ammonia/air=1/1.2/10
Table 1
| Embodiment | Catalyst is formed | The preparation committed step | Conversion of propane % | Acrylonitrile selectivity % |
| Embodiment 1 | Mo lV 0.31Nb 0.22Te 0.23O x | Acid is sulfuric acid, and the pH value of mixed solution is 1 | 56.2 | 54.5 |
| Comparative example 1 | Mo lV 0.31Nb 0.22Te 0.23O x | No acid for adjusting pH value | 46.6 | 30.3 |
| Comparative example 2 | Mo lV 0.31Nb 0.22Te 0.23O x | Acid is sulfuric acid, and the pH value of mixed solution is 4, roasting in the air | 8.2? | 4.6? |
| Comparative example 3 | Mo lV 1.1Nb 0.11Te 0.23O x | No acid for adjusting pH value, roasting in the air | 7.6 | 4.4 |
| Embodiment 2 | Mo lV 0.31Nb 0.22Te 0.23O x | Acid is nitric acid, and the pH value of mixed solution is 1.5 | 52.9 | 48.6 |
| Embodiment 3 | Mo lV 0.25Nb 0.22Te 0.23O x | Roasting in 500 ℃ of nitrogen | 51.8 | 49.2 |
| Embodiment 4 | Mo lV 0.31Nb 0.11Te 0.17O x | Acid is sulfuric acid, and the pH value of mixed solution is 2 | 50.3 | 53.4 |
| Embodiment 5 | Mo lV 0.61Nb 0.03Te 0.53W 0.02O x | Roasting is 4 hours in 700 ℃ of nitrogen | 50.4 | 48.4 |
| Embodiment 6 | Mo lV 0.31Nb 0.22Te 0.23O x | Acid is sulfuric acid, and the pH value of mixed solution is 1, and successive reaction is after 30 days | 55.1? | 53.9? |
The stable appraisal result of embodiment 6 and comparative example 1 sees Table 2
Table 2
Claims (5)
1. catalyst that is used for alkane ammoxidation reaction, form by silica supports with the oxide that atomic ratio measuring is expressed as following general formula:
MoV
aNb
bTe
cO
x
Wherein, the span of a is 0.1～1.0;
The span of b is 0.01～1.0;
The span of c is 0.01～1.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
The consumption of carrier silica is 30～70% of catalytic amount by weight percentage in the catalyst;
This Preparation of catalysts comprises the steps:
1) with aequum Mo and corresponding salt of Te or the oxide solution I of making soluble in water;
2) with corresponding salt of aequum V or the oxide solution II of making soluble in water;
3) with corresponding salt of aequum Nb or the oxide solution III of making soluble in water;
4) aequum is selected from HNO
3Or H
2SO
4In at least a acid solution IV of making soluble in water;
5) solution II is joined in the solution I, successively solution III and solution IV are joined wherein again, regulating mixed pH value of solution value is 1～4, the Ludox that adds aequum at last, make the slurry of catalyst, this slurry stirs down evaporation at 80～180 ℃ and obtains viscous paste always, and is dry then, temperature be in 400～800 ℃ the inert atmosphere roasting 0.5～8 hour the alkane ammoxidation catalyst.
2. the catalyst that is used for alkane ammoxidation reaction according to claim 1, the pH value that it is characterized in that mixed solution is 1～3.
3. the catalyst that is used for alkane ammoxidation reaction according to claim 1 is characterized in that sintering temperature is 500～700 ℃.
4. the catalyst that is used for alkane ammoxidation reaction according to claim 1 is characterized in that inert atmosphere is a nitrogen.
5. the catalyst that is used for alkane ammoxidation reaction according to claim 1 is characterized in that roasting time is 1～4 hour.
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| CN101279252B true CN101279252B (en) | 2011-05-18 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884918B (en) * | 2009-05-13 | 2012-09-05 | 中国石油化工股份有限公司 | Method for preparing antimony-containing catalyst used for ammoxidation of alkane |
| CN101992106B (en) * | 2009-08-31 | 2012-11-14 | 中国石油化工股份有限公司 | Alkane ammoxidation catalyst |
| CN101797510B (en) * | 2010-04-02 | 2012-07-25 | 华东理工大学 | Catalyst containing rare earth for ammoxidation of alkane |
| CN103736496B (en) * | 2012-10-17 | 2015-10-21 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method |
| CN103028420B (en) * | 2013-01-08 | 2014-11-26 | 中国科学院生态环境研究中心 | Iron-tungsten-titanium composite oxide catalyst, and preparation method and purpose thereof |
| MY165608A (en) * | 2015-03-31 | 2018-04-16 | Asahi Chemical Ind | Method for producing oxide catalyst, and method for producing unsaturated nitrile |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491745A (en) * | 2002-10-01 | 2004-04-28 | ��������ķ������ | Mo-V-M-Nb-X oxide catalyst for selective hydrocarbon oxidation synthesied by water heat |
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2007
- 2007-04-04 CN CN2007100390411A patent/CN101279252B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491745A (en) * | 2002-10-01 | 2004-04-28 | ��������ķ������ | Mo-V-M-Nb-X oxide catalyst for selective hydrocarbon oxidation synthesied by water heat |
Non-Patent Citations (1)
| Title |
|---|
| Hiromu Watanabe, et al..New synthesis route for Mo-V-Nb-Te mixed oxides catalyst forpropane ammoxidation.Applied catalysis A: General.2000,479-485. * |
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