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CN101992107A - Method for preparing catalyst for alkane ammonia oxidation reaction - Google Patents

Method for preparing catalyst for alkane ammonia oxidation reaction Download PDF

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Publication number
CN101992107A
CN101992107A CN2009100577997A CN200910057799A CN101992107A CN 101992107 A CN101992107 A CN 101992107A CN 2009100577997 A CN2009100577997 A CN 2009100577997A CN 200910057799 A CN200910057799 A CN 200910057799A CN 101992107 A CN101992107 A CN 101992107A
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catalyst
preparation
solution
aequum
alkane
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CN101992107B (en
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张顺海
缪晓春
汪国军
吴粮华
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • 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 method for preparing a catalyst for alkane ammonia oxidation reaction, which mainly solves the problems that the catalyst is formed nonuniformly, Te is volatile, the preparation technology is complex, the preparation environment is unstable, and active ingredients of the catalyst are volatile so as to cause low stability of the catalyst. A Mo-V-Nb-Te or Sb base is taken as a main component of the catalyst, and the catalyst comprises a silicon dioxide carrier and a composition with a general formula of MoVaNbbCcDdOx in an atomic ratio, wherein C is at least one of Te or Sb, and D is one of Sn, Ti, Fe, Bi, Al or W. A spray drying method is adopted, and the problems are solved by a technical scheme that a reducing agent is added in the preparation process to change the preparation environment, namely corresponding salt or oxides of Mo, Te or Sb are dissolved, solution of corresponding salt or oxides of V and Nb is respectively added, a needed amount of reducing agent is added to regulate an oxidation state, and a needed amount of silica sol is added for performing spray drying. The method can be applied to industrial production of preparing unsaturated nitriles by alkane ammonia oxidation.

Description

The preparation method of alkane ammoxidation reaction catalyst
Technical field
The present invention relates to a kind of preparation method of alkane ammoxidation reaction catalyst.Especially about a kind of propane ammoxidation acrylonitrile production or iso-butane prepared by ammoxidation methacrylonitrile Preparation of catalysts method.
Background technology
Manage the ammoxidation of propylene technology of the most of BP/Sohio of employing of production of present acrylonitrile, 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.
The present invention alkane ammoxidation system α different from the past, the place of alpha, beta-unsaturated nitriles Preparation of catalysts method is: 1. catalyst is formed simply, and raw material is easy to get; 2. Preparation of Catalyst good reproducibility, forming degree is good, and the catalyst yield height that makes has good stability, and reaction temperature is low, can be used in the industrial production.
Summary of the invention
Technical problem to be solved by this invention is to overcome all to exist Sb backflow to cause complicated process of preparation and yield not high in the prior art document, Te is volatile to cause problems such as catalyst stability is bad, and a kind of preparation method of alkane ammoxidation reaction catalyst is provided.This shaping of catalyst degree is good, 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.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of alkane ammoxidation reaction catalyst, contain silica supports and comprise the composition of following general formula with atomic ratio measuring:
MoV aNb bC cD dO x
Wherein, C is selected from least a among Te or the Sb, and D is selected from a kind of among Sn, Ti, Fe, Bi, Al or the W;
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;
The span of d is 0～1.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst;
This Preparation of catalysts comprises the steps:
1) with aequum Mo and Te or corresponding salt of Sb 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) with corresponding salt of aequum D or the oxide solution (IV) of making soluble in water;
5) aequum is selected from the reducing agent solution (V) of making soluble in water of oxalic acid, hydrazine hydrate, tartaric acid, pyruvic alcohol;
6) solution (II) is joined in the solution (I), successively solution (III), solution (IV) and solution (V) are joined wherein again, the Ludox that adds aequum at last, make the slurry of catalyst, this slurry stirred is evaporated to behind the required solid content spray-drying under 200～400 ℃ of inlet temperatures, temperature be in 400～800 ℃ the inert atmosphere roasting 0.5～8 hour the alkane ammoxidation catalyst.
In the technique scheme, reducing agent is preferably at least a or its mixture in oxalic acid and the pyruvic alcohol, slurry solid content preferable range is 25～50% before the spray-drying, spray-drying inlet temperature preferable range is 250～380 ℃, catalyst sintering temperature preferable range is 500～700 ℃, calcination atmosphere is preferably 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, the most handy corresponding oxide of antimony component, hydroxide or its ammonium salt; 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 390～430 ℃.
Though catalyst of the present invention is formed simple, but owing to improved the Preparation of catalysts method, adopt spray drying process, in preparation process, regulate the oxidation state of oxide by adding reducing agent, make that thereby generating crystal between Te or Sb, the Mo obtains good catalyst stability, the catalyst that availability can be good.Preparation method's good reproducibility of the present invention, the catalyst that makes are used for propane ammoxidation reaction acrylonitrile yield up to 37%, and forming degree is good, the stability test result was good in 720 hours, acrylonitrile yield also remains on more than 34%, and reaction temperature is low to moderate 400 ℃, 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, 400 ℃ 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:
Figure B2009100577997D0000041
Figure B2009100577997D0000042
Figure B2009100577997D0000043
The invention will be further elaborated below by embodiment, but the present invention is not limited by following examples.
The specific embodiment
[embodiment 1]
72.1 gram ammonium heptamolybdates and 23.6 gram telluric acids are dissolved in the 300.0 gram hot water, make solution (I); 16.2 gram ammonium metavanadates are dissolved in the 333.0 gram hot water, make solution (II); 30.6 gram niobium oxalates are dissolved in the 85.0 gram hot water, make solution (III); 11.6 gram oxalic acid are dissolved in 20.0 grams make solution (IV) in the water.Under agitation solution (I) is joined in the solution (II), add solution (III) and solution (IV) more successively, add 250 gram weight concentration at last and be 40% Ludox, make the slurry of catalyst, it is 33% that this slurry stirring is evaporated to solid content, be 350 ℃ of following spray-dryings in inlet temperature then, roasting is 2 hours in 600 ℃ of nitrogen atmospheres, can get propane ammoxidation catalyst 50%Mo 1V 0.34Nb 0.24Te 0.25O x+ 50%SiO 2, get 20～40 orders behind the compressing tablet and carry out the fixed bed micro anti-evaluation.
[comparative example 1]
14.4 gram ammonium heptamolybdates and 4.72 gram telluric acids are dissolved in the 40.0 gram hot water, make solution (I); 3.24 gram ammonium metavanadates are dissolved in the 70.0 gram hot water, make solution (II); 6.12 gram niobium oxalates are dissolved in the 17.0 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 50%Mo 1V 0.34Nb 0.24Te 0.25O 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
400 ℃ 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
Figure B2009100577997D0000061
The stable appraisal result of embodiment 1 and comparative example 1 sees Table 2
Table 2
Figure B2009100577997D0000062

Claims (7)

1. the preparation method of an alkane ammoxidation reaction catalyst, contain silica supports and comprise the composition of following general formula with atomic ratio measuring:
MoV aNb bC cD dO x
Wherein, C is selected from least a among Te or the Sb, and D is selected from a kind of among Sn, Ti, Fe, Bi, Al or the W;
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;
The span of d is 0～1.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30～70% by weight percentage in the catalyst;
This Preparation of catalysts comprises the steps:
1) with aequum Mo and Te or corresponding salt of Sb 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) with corresponding salt of aequum D or the oxide solution (IV) of making soluble in water;
5) aequum is selected from the reducing agent solution (V) of making soluble in water of oxalic acid, hydrazine hydrate, tartaric acid, pyruvic alcohol;
6) solution (II) is joined in the solution (I), successively solution (III), solution (IV) and solution (V) are joined wherein again, the Ludox that adds aequum at last, make the slurry of catalyst, this slurry stirred is evaporated to behind the required solid content spray-drying under 200～400 ℃ of inlet temperatures, temperature be in 400～800 ℃ the inert atmosphere roasting 0.5～8 hour the alkane ammoxidation catalyst.
2. the preparation method of alkane ammoxidation reaction catalyst according to claim 1 is characterized in that reducing agent is at least a or its mixture in oxalic acid and the pyruvic alcohol.
3. the preparation method of alkane ammoxidation reaction catalyst according to claim 1 is characterized in that the preceding slurry solid content of spray-drying is 25～50%.
4. the preparation method of alkane ammoxidation reaction catalyst according to claim 1 is characterized in that the spray-drying inlet temperature is 250～380 ℃.
5. the preparation method of alkane ammoxidation reaction catalyst according to claim 1 is characterized in that sintering temperature is 500～700 ℃.
6. the preparation method of alkane ammoxidation reaction catalyst according to claim 1 is characterized in that inert atmosphere is a nitrogen.
7. the preparation method of alkane ammoxidation reaction catalyst according to claim 1 is characterized in that roasting time is 1～4 hour.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549224A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Unsaturated nitrile catalyst and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1262235A3 (en) * 2001-05-23 2003-04-16 Rohm And Haas Company Mixed-metal oxide catalysts containing molybdenum and vanadium and processes for preparing the same
US6919295B2 (en) * 2002-05-01 2005-07-19 Rohm And Haas Company Supported mixed metal oxide catalyst
CN101306376B (en) * 2007-05-16 2010-05-19 中国石油化工股份有限公司 Tellurium containing alkane ammoxidation reaction catalyst
CN101428230B (en) * 2007-11-07 2010-12-08 中国石油化工股份有限公司 Catalysts for the ammoxidation of alkanes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549224A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Unsaturated nitrile catalyst and preparation method thereof
CN104549224B (en) * 2013-10-28 2017-09-15 中国石油化工股份有限公司 Unsaturated nitrile catalyst and preparation method thereof

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